Distribution Of Carbon Isotopes Research Articles

Fingerprinting Organofluorine Molecules via Position-Specific Isotope Analysis.

Organofluorine substances are found in a wide range of materials and solvents commonly used in industry and homes, as well as pharmaceuticals and pesticides. In the environment, organofluorine molecules are now recognized as an important class of anthropogenic pollutants. Fingerprinting organofluorine compounds via their carbon isotope ratios (13C/12C) is crucial for correlating molecules with their source. Here we apply a 19F nuclear magnetic resonance spectroscopy (NMR) technique to obtain the first position-specific carbon isotope ratios for a diverse set of organofluorine molecules. In contrast to traditional isotope ratio mass spectrometry, the 19F NMR method provides 13C/12C isotope ratios at each carbon position where a C-F bond is present, and does not require fragmentation or combustion to CO2, overcoming challenges posed by the robust C-F covalent bonds. The method was validated with 2,2,2-trifluoroethanol, and applied to analyze heptafluorobutanoic acid, 5-fluorouracil and fipronil. Results reveal distinct intramolecular carbon isotope distributions, enabling differentiation of chemically identical molecules. Notably, the NMR method accurately analyzes carbon isotopes within target molecules despite impurities. Potential applications include the detection of counterfeit products and drugs, and ultimately pollution tracking in the environment.

Exploring the potential of stable isotope methods for identifying the origin of CO2 in the carbonation process of cementitious materials within the carbon capture and storage environment

This study investigates the potential of stable isotope (δ13C) methods for exploring the carbonation process of cementitious materials, including well cement paste, portlandite (CH), and calcium silicate hydrate (C–S–H). Through comprehensive chemical and isotopic characterization, along with extensive data analysis, several key conclusions emerge. Firstly, the pH of the solution, as well as the solubility and pH characteristics of mineral phases (CH and C–S–H), are identified as influential factors impacting the kinetics, thermodynamics, and distribution of carbon isotopes (12C and 13C) during the reaction process. Secondly, the study uncovered that higher final pH values correlated with a DIC pool enriched with 13C and a higher εDIC-CO2 isotopic enrichment factor (10.7–12.6 ‰). Furthermore, higher levels of DIC content, solution electrical conductivity, and lower pH lead to higher δ13C–CaCO3 and greater εCaCO3-DIC isotope fractionation (−12.9 to −7.5 ‰). These conditions favor the formation of carbonate minerals with higher isotopic signature (δ13C–CaCO3), thus better preserving the δ13C-DIC isotope ratio. It was identified that the carbonate mineral (δ13C–CaCO3) formed through the carbonation of cementitious materials (class G cement, CH, and C–S–H) appears to preserve the isotopic signature of the δ13C–CO2 source. In conclusion, stable isotope methods could be a valuable tool for assessing and monitoring the cement carbonation process in Carbon Capture and Storage (CCS) wells, particularly when it is crucial to distinguish between injected and endogenous CO2.

Controls of carbon isotope fractionation during gas desorption in overmature marine shales

Carbon isotope fractionation serves as a crucial tool for assessing gas-in-place content and the gas-adsorbed ratio of shale gas during production. However, a significant gap exists in the understanding of the mechanism and impacts of diverse composition and organic matter on carbon isotope fractionation. To address this gap, this study conducted adsorption and desorption experiments on ten shale samples from the Longmaxi Formation. Various integrated analytical techniques were employed, encompassing X-ray diffraction, bitumen reflectance measurement, total organic carbon (TOC) content analysis, stable carbon isotope analysis, low-pressure gas adsorption tests, and field emission scanning electron microscopic observations. The results reveal that methane dominates the shale gas, with the carbon isotopes exhibiting a distinctive full reversal, attributed to the redox reaction between the ethane and water or transition metals. Differential adsorption capacities of shale led to varied carbon isotope distribution during desorption experiments. Increased micropore quantity in shale is anticipated to augment its adsorption capacity, while elevated feldspar content constrains adsorption due to the absence of intraparticle pores. Consequently, a negative correlation is observed between feldspar content and shale gas fractionation. Although intraparticle pores exist in carbon minerals, their connectivity and low carbonate content limit adsorption capacity in clay-rich shale. Deep burial depletes slit pores in clay minerals, resulting in a low adsorption capacity in clay-rich shale. Notably, the over-mature stage exhibits a substantial increase in micropores within organic matter, positively correlating with carbon isotope fractionation. The positive correlation between quartz content and TOC content is attributed to the positive relationship between the quartz content and carbon isotope fractionation. Additionally, the isotopic values of desorbed gas exhibit significant variability when TOC content exceeds 2.0%, remaining stable when TOC content is less than 2.0%.

Pyrolysis experiments of model compounds to explore carbon isotope fractionation in propane from natural gas

Investigating the mechanisms that determine the bulk and position-specific carbon isotopic distributions of propane in natural gas will help elucidate its formation and evolution. We used octadecane and squalane as model compounds that give simple precursors for gas production in gold-tube isothermal pyrolysis experiments to study the variations in intermolecular and intramolecular distributions of isotopes in the generated gaseous hydrocarbons. The δ13C values of the products and inverses of their carbon numbers (1/n where n = C1–C5) showed a negative linear relationship versus maturity, indicating that they formed by homolytic cleavage of C–C bonds and that the precursors showed homogeneous distributions of carbon isotopes. However, the significant difference in the kinetic isotopic effects (KIEs) of the gas generated by cracking of two model compounds under the same experimental conditions is not readily explained by single homolytic bond cleavage. The results indicate that besides the KIE of C–C bond cleavage, the bulk and position-specific carbon isotopic compositions of propane are related to the chemical and isotopic structures of the precursors and the propane transformation ratio. Based on the sites of C–C bond cleavage, two isotopic fractionation patterns (i.e., normal propyl and isopropyl models) may explain the bulk and position-specific carbon isotopic distributions of the generated propane. According to the propyl model, propane originates from (normal) propyl structures (CH3CH2CH2*) in the precursor via C–C bond cleavage at a terminal site of a propyl group, while the isopropyl model involves propane derived from isopropyl structures (CH3CH*CH3) in the precursor, with C–C bond cleavage at the central site. Simulations show that these distributions for propane cracked from octadecane closely follow the propyl model, whereas propane generated from squalane showed mixed contributions from both models, and its bulk and position-specific carbon isotopic distributions depend on the proportions of propyl and isopropyl structures in the precursors. Variations of propane’s position-specific carbon isotopic distributions during the main stage of propane generation indicate that free radical reactions are the main pathway for thermogenic propane formation, resulting in similar KIEs for propane terminal and central carbons. Therefore, the position-specific carbon isotopic distribution of propane can provide evidence of its formation mechanism and shows potential for revealing the origin and evolution of natural gas.

Laser Ablation-Capillary Absorption Spectroscopy: A novel approach for high throughput and increased spatial resolution measurements of δ13C in plant-soil systems

Spatial and temporal heterogeneity of nutrient exchange within the rhizosphere is a topic of increasing interest, although challenging to study due to limits in existing analytical capabilities. Here, we developed and demonstrated a new approach applying laser ablation sample introduction to capillary absorption spectroscopy (LA-CAS) to characterize carbon isotopic distribution within plant tissues, rhizosphere, and soil. We exposed switchgrass plants to 13CO2 to allow tracing of 13C-labeled photosynthates within plant biomass and into the associated soil. The LA-CAS methods we describe leverage continuous measurements of a sample stream derived from laser ablation line scans (10–25 μm in width) over a sample surface which enables the user to produce an isotope map with a) higher data density or b) over larger spatial areas versus previously existing techniques. This versatility of LA-CAS is assessed through testing of a range of laser parameters (spot size, scan rates) on various materials (soil, plant biomass/tissues, and rhizosphere). We demonstrate the ability of LA-CAS to provide near instantaneous δ13C measurements over isotopically distinct surfaces to enable high spatially resolved mapping of 13C-labeled material within the rhizosphere. Applying LA-CAS analysis to plant biomass, we observed higher δ13C values concentrated within phloem structures, consistent with localized photosynthate transport. When mapping across the rhizosphere, 13C-enriched soil was typically present within 5–10 μm of root boundaries with a steep spatial increase in δ13C when the scan approached the middle of the root. As with all LA approaches, care is required to ensure accurate results as phenomena linked to ablation, combustion, and isotopic measurement can impart artifacts if not carefully controlled. Still, taken as a whole, our demonstrations highlight the increased sample throughput, improved data density, and enhanced δ13C capability of LA-CAS versus other LA techniques and emphasize the role this method can play in future plant and rhizosphere related studies.

Origin and Geological Significance of Residual Oil in High-Angle Joint Fissures: A Case Study of the Nadu Formation in Baise Basin, South China

The Baise Basin is a Paleogene pull-apart basin with numerous strike-slip faults which are not favorable for hydrocarbon preservation. The Nadu Formation, research object of this paper, is generally rich in oil and contains a large number of high-angle joint fissures. Analyzing the origin of residual oil in high-angle joint fissures can reveal the hydrocarbon migration and accumulation characteristics of the pull-apart-type basins. Molecular geochemical composition characteristics of crude oil and oil source of the Nadu Formation were discussed based on the saturated hydrocarbon biomarker compound and stable carbon isotope distribution of n-alkanes. The studied samples were selected from four members (E2n1, E2n2, E2n3up, and E2n3low) of the Nadu Formation. The results suggested that the average oil content of E2n1 fissures is 0.32 mg/cm2, and the oil distribution is not uniform. The distribution of oil on the fissures of E2n2 and E2n3 is uniform and complete, and the oil content reaches 0.53 mg/cm2. The oil in the joint fissures of the Nadu Formation is heavy, as the light hydrocarbon is seriously lost during migration. Thus, the oil in the joint fissures is residue after crude oil loses light components during migration. By comparing the molecular biomarker characteristics and stable carbon isotopic compositions, crude oil of the Nadu Formation can be classified into three categories: E2n1, E2n2 + E2n3up, and E2n3low. The E2n1 oils have the lowest maturity and are sourced from the E2n1 source rocks. Moreover, the maturity of E2n2 and E2n3 samples are relatively high. Biomarker and carbon isotope characteristics of the E2n2 and E2n3up oils are similar, indicating that they are derived from the E2n2 + E2n3up source rocks. The E2n3low oils are the mixture of the crude oil generated from the E2n3up source rocks and the E2n3low source rocks. Results presented show that the residual oil of high-angle joint fissures in the Nadu Formation is contributed by adjacent source rocks. The crude oil discharged from the Nadu Formation can only migrate upward along high-angle joints in a short distance, and the migration distance is usually less than 5 m. In conclusion, although the Nadu Formation has developed a large number of high-angle joint fissures, crude oil in the Nadu Formation has not vertically migrated for long distance along the joint fissures. The well-preserved fractures as important shale oil storage spaces indicate that the Nadu Formation has good shale oil exploration potential. The results may provide insights into the origins of hydrocarbons in the Nadu Formation from the Baise Basin and enhanced knowledge for optimizing future exploration and production.

Stable carbon isotope and n-alkane distributions in sediment cores from saline and freshwater Gabu lakes, southeast Nigeria: environmental implications

Stable carbon isotope and n-alkane distributions in sediment cores from saline and freshwater Gabu lakes, southeast Nigeria: environmental implications

A New Natural Gas Accumulation Model in the Triassic Xujiahe Formation: A Case Study in the Tongjiang-Malubei Area of the Sichuan Basin

The natural gas in the Triassic Xujiahe Formation (T3x) is reported to be mainly derived from the T3x source rock itself. Here, we report a new natural gas accumulation model, which demonstrates that the T3x gas in the Tongjiang-Malubei (TM) area is derived from both T3x and underline marine source rocks. The T3x gas in the TM area is characterized by CH4 with a gas dryness coefficient above 0.99, indicating a high thermal maturity. The δ13C values of the methane, ethane, and propane in the T3x gas in the TM area are −33.7~−29.2‰, −32.7~−28.3‰, and −32.8~−29.5‰, respectively. Compared with the T3x gas in the Yuanba area, which was sourced from the T3x source rock, the T3x gas in the TM area contains heavier δ13C in methane and lighter δ13C in ethane, showing a partial reversal carbon isotope distribution (δ13C1 > δ13C2). According to their chemical and isotopic compositions, the T3x gas in the TM area was a mixture of coal-type and oil-type gases. The coal-type gas was mainly derived from the type III kerogen of the T3x source rock, and the oil-type gas was derived from the type-I kerogen of marine source rock in the Permian Wujiaping Formation (P3w). The oil-type gas migrated upward along the deep-seated faults that connect the P3w source rock and T3x sandstone reservoirs, and then mixed with coal-type gas in the T3x reservoirs, resulting in large-scale gas accumulation. This new gas accumulation model is controlled by a dual gas source supply and a high efficiency migration via the fault system. The findings of this study can help us to better understand the gas accumulation mechanism with the development of late-stage penetrating faults, which not only have implications for future petroleum exploration and development in the TM area, but also affect other analogous areas in the Sichuan Basin.

Kinetic isotope effect and reaction pathways of thermogenic propane generation at early maturation stage: Insights from position-specific carbon isotope distribution

An intramolecular isotopic study was conducted on natural gases from the Turpan-Hami Basin of China. The set of natural gases exhibits larger δ13C values of the terminal position compared with those at the central position of propane, with ΔC-T (δ13Ccentral-δ13Cterminal) values ranging from −3.8‰ to −0.7‰. During the thermal cracking of kerogen, the primary kinetic isotope effect is on the terminal carbon position to generate n-propyl radicals and on the central carbon position to produce i-propyl radicals. Therefore, distinct reaction pathways significantly influence the position-specific carbon isotope distribution in thermogenic propane. In the early stage of maturation, propane is preferentially generated from the i-propyl radicals by capturing hydrogen atoms owing to the lower dissociation energies of i-propyl radicals cleavage from kerogen compared with those of n-propyl radicals, resulting in larger δ13C values in the terminal position compared with those at the central position of generated propane. The position-specific 13C isotope composition of propane could provide new insights into revealing the generation mechanism of natural gas in the geological period at the atomic level.

Graphitic inclusions in zircon from early Phanerozoic S-type granite: Implications for the preservation of Hadean biosignatures

A biotic origin of isotopically light graphite in Hadean zircon remains contested, in part because it is unclear how biogenic carbon in sediments behaves during diagenesis, metamorphism and anatexis, and how it can be preserved as inclusions in zircon. Here, we report the discovery of graphitic inclusions in zircon from Rumburk granite in the Lusatian Block of eastern central Europe as the first example of such inclusion-bearing zircon in a well-constrained geological and petrological context. Most graphite inclusions are trapped at the interface between inherited zircon interiors of early Cambrian–Proterozoic age and late Cambrian (496.2 ± 2.3 Ma; 95% confidence) zircon overgrowths that crystallized at ∼700 °C under highly reducing conditions (typically −4.6 log units relative to the fayalite-magnetite-quartz buffer). Zircon overgrowths are also enriched in xenotime component (up to 93 µmol/g P) and δ18O (average δ18O = 7.7‰), both typical for S-type granitic melts. Raman microspectroscopy reveals crystalline and disordered graphitic carbon, but because overgrowth temperatures reached >700 °C, sufficient for complete graphitization, disordering is presumably secondary and caused by in-situ irradiation from the zircon host. Because organic materials were avoided during sample preparation, and inclusions were excavated by ion beam sputtering, exposure to potential C-bearing contaminants can be dismissed. Inclusions range in δ13C from −44.6 to −7.5‰ with a dominant mode at δ13C = −34‰ that is positively skewed. Rayleigh-type graphite precipitation from a CO2-CH4 fluid with a starting composition equivalent to regional black shale (δ13C = −32‰) explains inclusion carbon isotopic range and distribution. Collectively, these observations suggest that graphite was initially trapped in voids formed via dissolution-reprecipitation of trace element enriched, and possibly metamict, detrital zircon in metasedimentary protoliths when exposed to C-O-H fluids during prograde metamorphism. Subsequently, graphite-filled voids in inherited zircon became enclosed when zircon rims crystallized from highly reduced S-type granitic melts. Besides partial disordering of graphitic carbon due to irradiation, there is no indication for post-entrapment alteration, demonstrating that graphitic inclusions in zircon can preserve isotopic biosignatures over hundreds of millions of years.

Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy.

Intramolecular or position-specific carbon isotope analysis of propane (13CH3-12CH2-12CH3 and 12CH3-13CH2-12CH3) provides unique insights into its formation mechanism and temperature history. The unambiguous detection of such carbon isotopic distributions with currently established methods is challenging due to the complexity of the technique and the tedious sample preparation. We present a direct and nondestructive analytical technique to quantify the two singly substituted, terminal (13Ct) and central (13Cc), propane isotopomers, based on quantum cascade laser absorption spectroscopy. The required spectral information on the propane isotopomers was first obtained using a high-resolution Fourier-transform infrared (FTIR) spectrometer and then used to select suitable mid-infrared regions with minimal spectral interference to obtain the optimum sensitivity and selectivity. We then measured high-resolution spectra around 1384 cm-1 of both singly substituted isotopomers by mid-IR quantum cascade laser absorption spectroscopy using a Stirling-cooled segmented circular multipass cell (SC-MPC). The spectra of the pure propane isotopomers were acquired at both 300 and 155 K and served as spectral templates to quantify samples with different levels of 13C at the central (c) and terminal (t) positions. A prerequisite for the precision using this reference template fitting method is a good match of amount fraction and pressure between the sample and templates. For samples at natural abundance, we achieved a precision of 0.33 ‰ for δ13Ct and 0.73 ‰ for δ13Cc values within 100 s integration time. This is the first demonstration of site-specific high-precision measurements of isotopically substituted non-methane hydrocarbons using laser absorption spectroscopy. The versatility of this analytical approach may open up new opportunities for the study of isotopic distribution of other organic compounds.

Geochemical characteristics of source rocks and gas exploration direction in Shawan Sag, Junggar Basin, China

In recent years, significant advancements have been achieved in the exploration of natural gas around Shawan Sag in the Junggar Basin. However, the geochemical characteristics and distribution of source rocks in the center of the sag have yet to be thoroughly researched, and there is a lack of understanding regarding the evolution history of hydrocarbon generation and the characteristics of each set of source rocks. This has posed limitations on future exploration and development initiatives in the area. The study focused on source rock samples from the uplift zone and conducted a comprehensive evaluation through seismic and hydrocarbon generation thermal simulation experiments. This allowed for clarification of the product characteristics of source rocks in different strata and pointing out the direction for future natural gas exploration. The results showed the presence of four sets of well-developed source rocks in Shawan Sag, characterized by their extensive thickness, wide distribution, and deep burial, laying a material foundation for oil and gas accumulation in peripheral structures. The Carboniferous and Jiamuhe Formation source rocks have high organic matter abundance, but the quality is poor and the potential for generating hydrocarbons is low, leading mainly to the generation of dry gas. On the other hand, the Fengcheng Formation and Lower Wuerhe Formation source rocks have high organic matter abundance and good quality, and are highly mature, resulting in high potential for generating hydrocarbons. The δ13C1-RO regression equation of natural gas in Shawan Sag was established, and the carbon isotope distribution patterns of ethane generated from source rocks in different layers were identified, providing a foundation for determining the maturity of natural gas and correlating the sources of gas in surrounding structures. The west slope of Shawan Sag has favorable preservation conditions and is located on a hydrocarbon migration pathway, similar to the slope of Mahu Sag. This area also has favorable geological conditions for the formation of large lithologic reservoirs, making it a key field for gas exploration in the study area moving forward.

The use of lntramolecular carbon isotope distributions (13c/12c) of biomolecules to study temporal organization of post-photosynthetic metabolism in a plant cell

It was found that the pyruvate decarboxylation reaction (PDR) plays a key role in post-photosynthetic metabolism, and PDR products are structural units involved in the synthesis of almost all its metabolites [1,2].

ANALYSIS OF RADIOCARBON DISTRIBUTION IN THE EUTROPHIC LAKE FISH ASSEMBLAGE USING STABLE C, N, S ISOTOPES

ABSTRACTThe carbon isotope distribution and its relationship with stable N and S isotope ratio values were investigated within a fish assemblage from the shallow lake Tapeliai, which is constantly affected by inflows of 14C depleted water from the surrounding watershed mires. The “conventional” radiocarbon age within the fish from this lake varied from 119 to 693 yr. The 14C/12C and δ13C values correlated significantly (r=0.85 p<0.001), which is not typical in lakes of the temperate zone. There were no observed statistical differences (Kruskal–Wallis ANOVA tests) in the 14C/12C values among different fish species. The radiocarbon dating values and 15N/14N measurements did not correlate. The radiocarbon measurement values also did not correlate with δ34S, however, the distribution of these isotopes in carp (119 yr and 1.3‰, respectively) and roach (344 yr and 4.5‰, respectively) indicated that fish may include allochthonous food sources in their diet.

Изотопия углерода индивидуальных ароматических соединений нефти для понимания их геохимии

The article analyzes published and original data related to the carbon isotopic composition of individual aromatic compounds of fossil organic matter and oil. It has been shown that there is reliable evidence of the intramolecular isotopic heterogeneity of a number of molecules. For example the isotopically depleted carbon of the methyl group of alkylnaphthalenes and the terminal methyl of n-alkanes. The 13C inheritance from the biochemical precursor during the aromatization is also well documented in the example of diterpenes in the series abietic acid — dehydroabietane — simonellite — retene, as well as in the other terpene and steroid series. At the same time, there is evidence of carbon isotopic fractionation during the formation of several aromatic compounds from a single precursor. The increasing aromatization of the prebuild polycyclic structure does not change the 13C value of the molecule, and the formation of aromatic compounds with different numbers of aromatic rings in competing reactions leads to isotope differentiation in accordance with the thermodynamically determined distribution of carbon isotopes. If the suggestion is correct, it is the key to the understanding of specific petroleum aromatic hydrocarbons formation mechanism. It is possible that a comparison of 13C values for pairs of compounds formed during the transformation of one precursor will also provide information on the temperature conditions for the occurrence of the corresponding reactions.

Biomarkers, light hydrocarbons, and diamondoids of petroleum in deep reservoirs of the southeast Tabei Uplift, Tarim Basin: Implication for its origin, alteration, and charging direction

The Atan Bulge in the southwestern Tabei Uplift of the Tarim Basin provides insights into the geochemistry of the oils and condensates in deep Ordovician reservoirs because its reservoir burial depth is generally greater than 6000 m. To investigate the oil origin, alteration, and migration pathways, the carbon isotopes, biomarkers, light hydrocarbons, and diamondoids of 16 oil and condensate samples from the Ordovician reservoirs in the Atan Bulge were analyzed. The results show that chain alkanes dominate the light hydrocarbons, followed by cycloalkanes and aromatic hydrocarbons. 1-methyladamantane (MA) dominates the diamondoids, followed by 1,3-dimethyldiamantane (DMD). The samples lacked biodegradation and thermochemical sulfate reduction signatures. Except for a few samples near the Manjiaer Depression, the evaporative fractionation caused by late natural gas charging is generally weak. The oil geochemistry suggests that the oils and condensates are primarily derived from lower Cambrian marine shale, and the organic matter is mainly type II. The equivalent vitrinite reflectance (Rc) calculated using thermal maturity indicators derived from methylphenanthrene, methyldiamantanes, and C5–C7 light hydrocarbons, respectively, is in the ranges of 0.78%–1.04%, 1.1%–1.5%, and 1.06%–1.48%. The samples' low (3-+4-)-methyldiamantane concentrations (36–76 μg/g) imply a low level of oil cracking. The carbon isotope distribution among oil fractions and different maturity ranges suggest that crude oil was generated and charged multiple times. The maturity of the samples decreases from SSE to NNE, indicating that the petroleum likely migrated from strike-slip faults during its primary charging period, with the Manjiaer Depression and its slope serving as the primary source kitchens.

Spatial distribution and environmental significance of modern organic carbon and nitrogen stable isotopes in the source area of the Yellow River: A case study of Gyaring Lake and Ngoring Lake

Organic carbon and total nitrogen isotopes (δ13Corg and δ15N) are useful for identifying sources of organic matter and for reconstructing environmental conditions in paleoecology and paleoclimatology. Gyaring Lake and Ngoring Lake are the two largest freshwater lakes in the source area of the Yellow River (SAYR), which lies in the northeastern the Qinghai–Tibet Plateau. These bodies of water were chosen as our research objects, and we analyzed the carbon and nitrogen isotopes in the surface sediments of the two lakes and in soil samples from around the lakes. The results indicate the consistency and endogenous characteristics of the organic matter sources of the distribution of δ13Corg and δ15N in the surface sediments of Gyaring Lake and Ngoring Lake. The δ13Corg values of the two lakes were significantly positive in areas near the inflow and outflow of the Yellow River. The distribution of δ15N in Gyaring Lake was similar to that of total organic carbon (TOC) and total nitrogen (TN), and its values were relatively higher than those affected by the joint influence of the Yellow River and some small tributaries, while δ15N was more positive in the deep-water area of Ngoring Lake. This study provides reliable and modern data on δ13Corg and δ15N for the long-term paleoenvironment and paleoecological reconstruction of the SAYR in the future.

Produced Gas and Condensate Geochemistry of the Marcellus Formation in the Appalachian Basin: Insights into Petroleum Maturity, Migration, and Alteration in an Unconventional Shale Reservoir

The Middle Devonian Marcellus Formation of North America is the most prolific hydrocarbon play in the Appalachian basin, the second largest producer of natural gas in the United States, and one of the most productive gas fields in the world. Regional differences in Marcellus fluid chemistry reflect variations in thermal maturity, migration, and hydrocarbon alteration. These differences define specific wet gas/condensate and dry gas production in the basin. Marcellus gases co-produced with condensate in southwest Pennsylvania and northwest West Virginia are mixtures of residual primary-associated gases generated in the late oil window and postmature secondary hydrocarbons generated from oil cracking in the wet gas window. Correlation of API gravity and C7 expulsion temperatures, high heptane and isoheptane ratios, and the gas geochemical data confirm that the Marcellus condensates formed through oil cracking. Respective low toluene/nC7 and high nC7/methylcyclohexane ratios indicate selective depletion of low-boiling point aromatics and cyclic light saturates in all samples, suggesting that water washing and gas stripping altered the fluids. These alterations may be related to deep migration of hot basinal brines. Dry Marcellus gases produced in northeast Pennsylvania and northcentral West Virginia are mixtures of overmature methane largely cracked from refractory kerogen and ethane and propane cracked from light oil and wet gas. Carbon and hydrogen isotope distributions are interpreted to indicate (1) mixing of hydrocarbons of different thermal maturities, (2) high temperature Rayleigh fractionation of wet gas during redox reactions with transition metals and formation water, (3) isotope exchange between methane and water, and, possibly, (4) thermodynamic equilibrium conditions within the reservoirs. Evidence for thermodynamic equilibrium in the dry gases includes measured molecular proportions (C1/(C1 − C5) = 0.96 to 0.985) and δ13C1 values significantly greater than δ13CKEROGEN. Noble gas systematics support the interpretation of hydrocarbon–formation water interactions, constrain the high thermal maturity of the hydrocarbon fluids, and provide a method of quantifying gas retention versus expulsion in the reservoirs.

δ13C in above-ground and below-ground organs of Spinulum annotinum (Lycopodiaceae)

• 12 C and 13 C isotope abundance in S. annotinum has been investigated for the first time. • δ 13 C value in S. annotinum is lower than that reported in other C 3 plants. • Different above- and below-ground S. annotinum organs have distinct δ 13 C values. • δ 13 C values of S. annotinum are connected with local plant diversity. Physiological processes in plants and plant–environment interactions can be analysed from the composition of stable carbon isotopes ( 13 C/ 12 C). This ratio can be indicated using the δ (delta) notation. Substantial evidence has been published in recent years demonstrating that post-photosynthetic fractionation occurs in plants and leads to differences in 13 C-enrichment in heterotrophic (as compared with autotrophic) organs. Yet our understanding of processes leading to 13 C divergence between leaves and heterotrophic tissues remains low. Large part of the isotope analysis is concerned with angiosperms, but not spore-bearing tracheophytes. In this study, we explored the 12 C and 13 C isotope distribution in above-ground and below-ground organs of an archaic lycophyte Spinulum annotinum (L.) A.Haines (interrupted clubmoss). The main objectives of this study were to determine the natural distribution of stable carbon isotopes in sporophytes of S. annotinum and to discuss possible causes for differences in δ 13 C. The study revealed that there are significant differences between δ 13 C in different S. annotinum organs. The δ 13 C values varied by about 2.4‰. The highest δ 13 C values were −30.0‰ in roots and the lowest were −32.4‰ in plagiotropic shoot leaves. The distance to a body of water had no significant effect on δ 13 C values in S. annotinum . Outgrowth size did not have a clear relationship with δ 13 C in S. annotinum . The Shannon Diversity Index was a significant predictor for δ 13 C values in S. annotinum . The uncovered δ 13 C and the relationship with abiotic habitat conditions and neighbouring plant species in the community provide a base for future lycophyte ecophysiology research.

Enhanced vertical mixing in the glacial ocean inferred from sedimentary carbon isotopes

Reconstructing the circulation, mixing and carbon content of the Last Glacial Maximum ocean remains challenging. Recent hypotheses suggest that a shoaled Atlantic meridional overturning circulation or increased stratification would have reduced vertical mixing, isolated the abyssal ocean and increased carbon storage, thus contributing to lower atmospheric CO2 concentrations. Here, using an ensemble of ocean simulations, we evaluate impacts of changes in tidal energy dissipation due to lower sea levels on ocean mixing, circulation, and carbon isotope distributions. We find that increased tidal mixing strengthens deep ocean flow rates and decreases vertical gradients of radiocarbon and δ13C in the deep Atlantic. Simulations with a shallower overturning circulation and more vigorous mixing fit sediment isotope data best. Our results, which are conservative, provide observational support that vertical mixing in the glacial Atlantic may have been enhanced due to more vigorous tidal dissipation, despite shoaling of the overturning circulation and increases in stratification.