Carbon Isotopic Composition Research Articles

Genetic variation in growth and leaf traits associated with local adaptation to climate in yellow birch (Betula alleghaniensis Britton)

Understanding patterns of variation in functional traits of hardwood trees is crucial for conserving and managing North American temperate forests under climate change. This study examined provenance variation of yellow birch ( Betula alleghaniensis Britton) in growth, biomass allocation, leaf morphology, and stable carbon isotope composition. Trees were grown from 10 seed sources originating from across Canada and the northern USA. Height and diameter were not significantly related to climate at seed origin, suggesting that variation may be better explained by site factors, such as soil pH and soil moisture. In contrast, carbon isotope composition and leaf morphological traits were significantly correlated to climate variables including temperature, precipitation, and solar radiation. Provenances from warmer, drier localities tended to have higher stable carbon isotope ratio (δ13C), greater specific leaf area, and narrower leaf width than their counterparts from cooler, wetter climates. Thus, variation in leaf morphological traits appears to be involved in adaptation of yellow birch to variation in temperature and moisture availability across the species’ range. Our results suggest that there may exist potential for selection and breeding of drought-resistant yellow birch genotypes to aid in reforestation under climate change.

Weak transport of atmospheric water-insoluble particulate carbon from South Asia to the inner Tibetan Plateau in the monsoon season

Carbonaceous particles play a crucial role in atmospheric radiative forcing. However, our understanding of the behavior and sources of carbonaceous particles in remote regions remains limited. The Tibetan Plateau (TP) is a typical remote region that receives long-range transport of carbonaceous particles from severely polluted areas such as South Asia. Based on carbon isotopic compositions (Δ14C/δ13C) of water-insoluble particulate carbon (IPC) in total suspended particle (TSP), PM2.5, and precipitation samples collected during 2020–22 at the Nam Co Station, a remote site in the inner TP, the following results were achieved: First, fossil fuel contributions (ffossil) to IPC in TSP samples (28.60 ± 9.52 %) were higher than that of precipitation samples (23.11 ± 8.60 %), and it is estimated that the scavenging ratio of IPC from non-fossil fuel sources was around 2 times that from fossil fuel combustion during the monsoon season. The ffossil of IPC in both TSP and PM2.5 samples peaked during the monsoon season. Because heavy precipitation during the monsoon season scavenges large amounts of long-range transported carbonaceous particles, the contribution of local emissions from the TP largely outweighs that from South Asia during this season. The results of the IPC source apportionment based on Δ14C and δ13C in PM2.5 samples showed that the highest contribution of liquid fossil fuel combustion also occurred in the monsoon season, reflecting increased human activities (e.g., tourism) on the TP during this period. The results of this study highlight the longer lifetime of fossil fuel-sourced IPC in the atmosphere than that of non-fossil fuel sources in the inner TP and the importance of local emissions from the TP during the monsoon season. The findings provide new knowledge for model improvement and mitigation of carbonaceous particles.

Carbon isotopes in the marine biogeochemistry model FESOM2.1-REcoM3

Abstract. In this paper we describe the implementation of the carbon isotopes 13C and 14C (radiocarbon) into the marine biogeochemistry model REcoM3. The implementation is tested in long-term equilibrium simulations where REcoM3 is coupled with the ocean general circulation model FESOM2.1, applying a low-resolution configuration and idealized climate forcing. Focusing on the carbon-isotopic composition of dissolved inorganic carbon (δ13CDIC and Δ14CDIC), our model results are largely consistent with reconstructions for the pre-anthropogenic period. Our simulations also exhibit discrepancies, e.g. in upwelling regions and the interior of the North Pacific. Some of these differences are due to the limitations of our ocean circulation model setup, which results in a rather shallow meridional overturning circulation. We additionally study the accuracy of two simplified modelling approaches for dissolved inorganic 14C, which are faster (15 % and about a factor of five, respectively) than the complete consideration of the marine radiocarbon cycle. The accuracy of both simplified approaches is better than 5 %, which should be sufficient for most studies of Δ14CDIC.

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy: Addressing issues arising from the laser-heating effects

The carbon isotopic composition of carbon dioxide fluid inclusions trapped within minerals reflects the origin and evolution of the CO2-bearing fluids and melts. Recently, we developed a highly accurate method using Raman spectroscopy to determine the carbon isotopic composition of CO2 fluid inclusions, by simultaneously collecting 13CO2 and hot bands at a controlled temperature, and using the peak height ratio of 13CO2 and one of hot bands near 1410 cm−1 (HR) to determine δ13C value. This microanalytical technique enables precise measurements of the δ13C values of different CO2 fluid inclusions within zoned mineral crystals to reveal the multiple-stages evolution of CO2-bearing fluids and melts. However, when studying fluid inclusions hosted within high laser heating coefficient minerals such as olivine and pyroxene in mantle xenoliths, local temperature near the inclusions will be higher than the temperature controlled by heating-cooling stage. To address this issue, we examined the effects of laser heating on CO2 isotopic standard samples sealed in the silica capillary, and developed a novel procedure to determine the δ13C values of natural fluid inclusions by using two CO2 standard samples with known carbon isotopic compositions. The proposed workflow successfully determines the δ13C values of natural CO2 inclusions, with an average deviation of 0.58 ‰ between the measurements and the model.

A discussion on carbon and oxygen isotopes of secondary carbonates in loess-paleosol sequences

Although carbon and oxygen isotopic compositions of carbonates are valuable for Quaternary climate reconstruction due to their sensitivity to paleoclimate changes, a comprehensive understanding regarding the formation, factors influencing isotopic variations, and age uncertainties of secondary carbonates in loess deposits remains elusive. This study investigates the microstructure and stable isotopes of secondary carbonates, specifically calcified root cells (CRC) and needle-fiber calcite (NFC), found within the loess deposits of the last glacial period in the northwestern region of the Chinese Loess Plateau. The average δ13C values of soil total organic matter, CRC, NFC, and total inorganic carbonates in the YuanBao sections are −22.1‰, −14.9‰, −7.0‰, −4.6‰, respectively. Radiocarbon dating results reveal that both CRC and NFC were not of synsedimentary origin. The pronounced negativity of the carbon isotopic composition and the microstructures offer insights that CRC formation is closely tied to C3 plants. The synchronous depletion of δ13CCRC and δ18OCRC values during the transition period from the last glacial to the Holocene, underscores the sensitivity of isotopic composition of CRC to local environmental changes, making it a potential candidate for paleo-climate studies. Additionally, CRC formed during the glacial period provides a close approximation to the true sedimentation age. The radiocarbon dating of NFC highlights a significant fluctuation in carbon source translocation depth, resulting in a pronounced temporal and spatial decoupling between NFC formation and the surrounding deposits. Consequently, values of δ13CNFC and δ18ONFC seem to exhibit no significant trend across the limited depth range in this research. We propose that, when using NFC for paleoclimate reconstruction, careful consideration of variations in translocation depths of carbon sources is imperative to prevent misestimations. NFC could potentially be more fitting for broader temporal-scale paleoclimate reconstructions rather than high-resolution investigations.

Ecophysiological traits of seedlings from different accessions of Stipa tenacissima along a climatic gradient

Predicting the future impact of climate change on Stipa tenacissima steppes is of paramount importance to prevent desertification. From this perspective, we selected seven populations, covering a rainfall range from 100 to 600 mm/year at the sites of seed collection, and we grew the seedlings at the same site. Gas exchange measurements of CO2, light response curves, chlorophyll content and isotopic analysis were investigated. Thala and Valencia populations displayed a contrasted gas exchange response. Both populations were subjected to A-Ci curve analysis. No significant difference was detected between these two different populations in the maximum rate of carboxylation (Vcmax) and the maximum rate of electron transport (Jmax). Stipa tenacissima exhibited a variable response in relation to different light intensities. Photosynthesis and chlorophyll fluorescence parameters proved to be significantly different among populations in response to light intensities. All populations exhibited similar chlorophyll content. The isotopic analysis highlighted a different carbon and nitrogen isotopic composition (δ13C and δ15N) and carbon content © among populations. Mesic populations presented a higher gas exchange activity and light response. The xeric populations performed a photosynthesis adjustment along with minimizing chlorophyll content. Under climate change, S. tenacissima limits productivity, which may lead to desertification.

Spatial distribution, environmental behavior, and health risk assessment of PAHs in soils at prototype coking plants in Shanxi, China: Stable carbon isotope and molecular composition analyses

To investigate the environmental behavior of and carcinogenic risk posed by 16 priority-controlled polycyclic aromatic hydrocarbons (PAHs), soil samples and air samples from the coke oven top were collected in two prototype coking plants (named PF and JD). The PF soils contained more PAHs than the JD soils because the PF plant employed the side-charging technique and had a lower coke oven height. The soils from both plants contained enough PAHs to pose a carcinogenic risk, and this risk was higher in the PF plant. Data were collected on the source characteristic spectrum of stable carbon isotopic composition (δ13C) of PAHs emitted from the coke oven top (δ13C values of −36.02‰ to −32.05‰ for gaseous PAHs and −34.09‰ to −25.28‰ for particulate PAHs), and these data fill a research gap and may be referenced for isotopic-technology-based source apportionment. Diagnostic ratios and isotopic technology revealed that the coking plant soils were mainly influenced by the coking process, followed by vehicle exhaust; the soils near the boundary of each plant were slightly affected by C3 plant burning. For most PAHs [excluding fluoranthene, benzo(k)fluoranthene, indeno(1,2,3-c,d)pyrene, and dibenzo(a,h)anthracene], the dominant migration process was the net volatilization of PAHs from soil to air. In the PF plant, 13C was depleted in gaseous PAHs during volatilization.

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.

Diversification in subsistence pattern of animal resources in the Hengduan Mountains: Multi‐isotopic evidence of Yingpanshan and Guijiabao site (5300–4000 cal. BP), China

AbstractThe Hengduan Mountains are located on the southeastern edge of the Qinghai‐Tibet Plateau, where farmers began to settle 6000 years ago. Animal husbandry plays a significant role in the sustenance economies of agricultural civilizations. It is unclear how Neolithic people acquired animal resources in the Hengduan Mountains. We explore animal geographical origins and feeding practices using the strontium, carbon, and oxygen isotope composition of tooth enamel at the Guijiabao and Yingpanshan sites during the Neolithic Age in the Hengduan Mountains. Multi‐isotopic evidence demonstrates that animals originate from several different regions with diverse foods. Guijiabao domestic dogs and pigs with a mixed C3/C4 diet share a similarly broad dietary spectrum with humans as enclosed animals, but the other pigs are wild boars with a C3 diet, likely free‐range animals or directly captured as meat resources. Yingpanshan dogs and pigs are both domestic animals with a mixed C3/C4 or C4‐based diet, but pigs with different 87Sr/86Sr ratios are likely raised by dispersed feeding modes. The inhabitants had diverse approaches for obtaining animal resources, including husbandry, hunting, and exchange. Diverse animal subsistence patterns are closely related to the complex geographical environment, reflecting the adaptation of farmers living in the high mountain valley regions.

Effects of lipid extraction on stable isotope ratios of carbon and nitrogen in muscles of freshwater fish

ABSTRACT The extraction of lipids by the Folch method from the muscles of all the fish studied led to statistically significant differences in the values of δ 15N. At the same time, lipid extraction led to a statistically significant increase in δ 13C in pike and roach, and to a statistically insignificant decrease in δ 13C in perch and bream. Thus, lipid extraction cannot serve as a universal method of sample preparation for the analysis of the isotopic composition of carbon (13C/12C) and nitrogen (15N/14N) in fish muscles. The differences between the δ 13C values in the samples before and after lipid extraction were statistically investigated by different models. It is shown that mathematical correction method models can be used, but the results are depending on the fish types.

Molecular and Carbon Isotopic Compositions of Crude Oils from the Kekeya Area of the Southwest Depression, Tarim Basin: Implications for Oil Groups and Effective Sources

Molecular and stable carbon isotopic compositions of 32 crude oils from the Kekeya area of the Southwest Depression, Tarim Basin, were analyzed comprehensively to clarify oil groups and trace oil sources. The results indicate that lacustrine shale sequences within the Upper-Middle Permian Pusige Formation (P3–2p) are the major effective oil sources; the thermal maturation effects exert the crucial impact on geochemical compositions of crude oils. In the Kekeya structural belt, crude oils produced from the Lower-Neogene, Middle-Paleogene and Middle-Cretaceous sandstone reservoirs were generated mainly from deeply buried P3–2p at the late-to-high maturity stage. These condensates are depleted in terpanes, steranes and triaromatic steranes and enriched in adamantanes and diamantanes. The evaluated thermal maturity levels of crude oils by terpanoids and steranes are generally lower than that of diamondoids, implying at least two phases of oil charging. In the Fusha structural belt, oils produced from the Lower-Jurassic reservoirs (J1s) of Well FS8 were generated from the local P3–2p at the middle to late mature stage. On the contrary, these oils are relatively rich in molecular biomarkers such as terpanes and steranes and depleted in diamondoids with only adamantanes detectable. The P3–2p-associated oils can migrate laterally from the Kekeya to Fusha structural belt, but not to the location of Well FS8. The Middle-Lower Jurassic (J1–2) lacustrine shales as the major oil sources are limited to the area around Well KS101 in the Kekeya structural belt. Crude oils originated from J1–2 and P3–2p can mix together within the Cretaceous reservoirs of Well KS101 by presenting the concurrence of high concentrations of terpane and sterane biomarkers and diamondoids as well as 2–4% 13C-enriched n-alkanes than those of P3–2p derived oils. This study provides a better understanding of hydrocarbon sources and accumulation mechanisms and hence petroleum exploration in this region.

Sources and transport of CO2 in the karst system of Jiguan Cave, Funiu Mountains, China

Conveyance and modification of carbon-isotope signals within the karst system remain difficult to constrain, due to the complexity of interactions between multiple components, including precipitation, bedrock, soil, atmosphere, and biota. Cave monitoring is thus critical to understanding both their transport in the karst system and dependence on local hydroclimatic conditions. Jiguan Cave, located in Funiu Mountain in central China, is representative of karst tourist caves with relatively thin epikarst zone. We conducted a comprehensive monitoring program of cave climate from 2018 to 2021 and measured δ13C during 2021 in monthly and heavy-rainfall samples of soil CO2, cave CO2, cave water (drip water and underground river), and underground river outlet. Our results demonstrate synchronous variations between CO2 concentration and δ13CCO2 in both soil and cave air on seasonal time scales. Cave pCO2 and carbon-isotope composition further exhibited a high sensitivity to human respiration with fluctuations of ~2000–3000 ppm within 4 days during the cave closure period in July 2021 without tourists. 13C-depleted isotopic signal of cave air in summer is the mixture of human respiration and soil CO2 which varies as a function of regional hydrological conditions of the summer monsoon during the rainy season with high temperatures and humidity. However, respired CO2 from the overlying soil was expected to be the only principal source of the cave CO2 when the anthropogenic CO2 source was removed. The high seasonal amplitude of cave air δ13CCO2 reflects ventilation dynamics, which leads to a prominent contribution from the external atmosphere during winter. Intriguingly, although the δ13C signal reflects complex vertical processes in the vertical karst profile, a heavy summer rainfall event was related to anomalously high δ13C values of cave water that can be utilized to interpret rainfall intensity and regional hydroclimate.

Assessment of Chalk as an Archive for the Lithium Isotope Composition of Seawater

AbstractThe understanding of silicate weathering and its role as a sink for atmospheric CO2 is important to get a better insight into how the Earth shifts from warm to cool climates. The lithium isotope composition (δ7Li) of marine carbonates can be used as a proxy to track the past chemical weathering of silicates. A high‐resolution δ7Li record would be helpful to evaluate the role of silicate weathering during the late Cretaceous climate cooling. Here, we assess chalk as a potential archive for reconstructing Late Cretaceous seawater Li isotope composition by comparing Maastrichtian chalk from Northern Germany (Hemmoor, Kronsmoor) to a Quaternary coccolith ooze from the Manihiki Plateau (Pacific Ocean) as a lithological analog to modern conditions. We observe a negative offset of 3.9 ± 0.6‰ for the coccolith ooze relative to the modern seawater Li isotope composition (+31.1 ± 0.3‰; 2SE; n = 54), a value that falls in the range of published offsets for modern core‐top samples and for brachiopod calcite. Further, the negative offset between the Li isotope compositions of Manihiki coccolith ooze and modern planktonic foraminifera is 2.3 ± 0.6‰. Although chalk represents a diagenetically altered modification of pelagic nannofossil ooze, manifested by changes in the composition of trace elements, we observe a consistent offset of Li isotope data between Maastrichtian chalk and Maastrichtian planktonic foraminiferal data (−1.4 ± 0. 5‰) that lies within the uncertainty of modern values. We therefore suggest that chalk can be used as a reliable archive for δ7Li reconstructions.

Stable isotope geochemistry evidences from fossil carbonate and sulfur minerals on the origin of geothermal water, Kızıldere Geothermal Field, Western Turkey

The Kızıldere geothermal field, located at the eastern part of the Büyük Menderes graben in Western Turkey, is the most important geothermal reservoir suitable for electricity generation. Current and fossil fumaroles and alteration zones are directly related to the tectonic zones influenced by N-S directional extension since Miocene period. Associated to fossil geothermal activities carbonate (calcite, dolomite) and sulfate (gypsum, anhydrite) minerals were occurred in the form of void/crack fill and bands/lenses parallel to bedding of Neogene clastic and carbonate rocks. The carbon (δ13CPDB ‰) and oxygen (δ18OPDB ‰) isotope compositions of hydrothermal calcites and dolomites and sulfur (δ34SCDT) and oxygen (δ18OSMOW) isotope compositions of gypsum and anhydrites are analyzed first time and correlated current geothermal water composition. The carbon and oxygen isotope data of calcites and dolomites have similar carbon but different oxygen isotope composition which increases in the direction of surface calcite – drill cuttings calcite – drill cuttings dolomite – surface dolomite. The isotope compositions of calcite and dolomite minerals range between limestone and marble host rock compositions and indicate the carbonate mineral-forming fluids originated from dissolution of carbonate rocks during the circulation of hot geothermal waters. According to the calcite-CO2 and dolomite-CO2 isotopic fractionation data for the 0–300 °C temperature range, the fossil isotope composition is higher than the composition of current CO2 and reflects relatively lower temperature conditions. The isotope compositions of gypsum and anhydrite minerals indicate that hot thermal waters dissolved terrestrial evaporites and formed a sulfur-rich geothermal solution, and hydrothermal gypsum and anhydrite precipitated from this solution. The δ34SCDT compositions of hydrothermal gypsum and anhydrites are similar to the current geothermal water compositions. Stable isotope geochemistry data of hydrothermal carbonate and sulfate minerals in the Kızıldere geothermal field have shown that the fluids forming these minerals were originated from host rocks instead of magmatic volatiles.

Soil Inorganic Carbon Formation and the Sequestration of Secondary Carbonates in Global Carbon Pools: A Review

Soil inorganic carbon (SIC), a potential carbon sink especially in arid and semi-arid environments, contributes to soil development, landscape stability, carbon (C) sequestration, and global C dynamics but due to the lack of SIC scientific reporting in most C sequestration research, its importance is unclear. A detailed overview of primary and secondary carbonate occurrence, formation, and importance is much needed to understand the role of pedogenic (PC)/secondary carbonate (a common biogeochemically derived soil mineral over time) in the SIC. The mechanisms involved in the formation of PC including carbon dioxide (CO2) from microbial respiration and precipitation, silicate mineral weathering, dissolution, and reprecipitation are highlighted. The isotopic composition of carbonates related to biological C3 or C4 carbon fixation pathways and other paleoecologic and/or climactic factors responsible for new soil carbonate formation are discussed in detail. To address the lack of knowledge associated with SIC, this review attempts to highlight the currently known aspects of the literature, and briefly describe the formation and methodologies that can aid in addressing the research gaps surrounding SIC sequestration. The authors also suggest that greater focus needs to be provided on the actual measurement of SIC to develop a more comprehensive SIC inventory to provide sound data for future research direction, and modeling efforts and to predict C terrestrial storage and change efficiently.

The relationship of plant leaf δ13Cn-alkanes and salinity in coastal ecosystems applied to palaeobotany: Case study from the Cenomanian of the Bohemian Cretaceous Basin, Czechia

Stable carbon isotopes in fossil leaf cuticles (n-alkanes, δ13Cn−alkanes) extracted from the sediment are widely used for palaeoenvironmental reconstructions. This approach relies on a series of assumptions (such as the plant-group-specific isotopic range, or the atmospheric CO2 being the major factor for the isotopic values) and leaves out the complexity of the carbon isotope fractionation within the plant through time, space, and different environments. The leaf cuticle is a unique archive of local environmental conditions, which has the potential to constrain individual plant habitat. To explore the applicability of the information gained from the δ13Cn−alkanes from fossil plants, a fossil coastal environment was studied.During the Cenomanian (100.5–93.9 Ma), the basal part of the Bohemian Cretaceous Basin, including locality Pecínov (Czechia), was formed as a result of sea transgression to the Palaeozoic Bohemian Massif triggered by the Alpine orogenesis. Coastal halophytic vegetation growing in this zone of prograding sea has no extant equivalent, and there are uncertainties associated with vegetation distribution or individual taxa habitat.Therefore, we examine the relationship between δ13Cn−alkanes extracted from individual leaves of coastal C3 plants (fossil and modern) and osmotic stress (salinity and drought) to reconstruct the individual plant habitat, thus, vegetation distribution in the coastal zone. We investigated modern mangrove and salt marsh vegetation in New Zealand and the United Kingdom, respectively, as well as transition zones (mangrove invading original salt marshes) for δ13C, soil moisture and salinity to build a calibration of the relationship, which is then applied to the Cenomanian fossil leaves from the locality of Pecínov.We found a positive correlation between water stress (caused by salinity or drought) and the δ13C values of n‐C25, n‐C27, n‐C29 and n‐C31 alkanes when combining all species from all modern localities. However, the absence of a strong correlation within individual species suggests a combination of several factors controlling the carbon isotopic composition. Nevertheless, the general response of δ13C to osmotic stress can be applied to compare the habitat of modern and fossil coastal plants. Thus, by using this relationship, we reconstructed the relative salinity and water stress of individual species of the Cenomanian plants by relating them to modern species-specific ranges of n‐C29 isotopic signatures.We showed that the δ13Cn−alkanes of fossil plant cuticles/leaves can be a valuable tool in the reconstruction of plant habitat and help us understand evolution of fossil environments in time and space. Additionally, our data further confirm that the δ13C acquired from plants should be used with caution when reconstructing global atmospheric CO2 because the osmotic stress can shift the δ13C in plants growing in terrestrial environments, particularly in coastal sea-influenced ecosystems.

Intramolecular carbon isotopic rollover in propane from natural gas reservoirs of the Santanghu Basin: Insights into chemical structure of kerogen

An intramolecular isotopic study was conducted on natural gases from the Santanghu Basin in China. Propane samples spanned a wide range of ΔC-T (δ13Ccentral-δ13Cterminal) values from –8.4 to 8.5 ‰, δ13Ccentral and δ13Cterminal values varied from –37.3 to –25.8 ‰ and –35.7 to –28.9 ‰, respectively. During thermal maturation, the position-specific carbon isotopic composition of propane shifted from δ13Ccentral < δ13Cterminal to δ13Ccentral > δ13Cterminal, and the δ13Cterminal decreased by 6.8 ‰ within a Ro range of 0.46–0.50 %. The intramolecular carbon isotopic rollover and a decrease in δ13Cterminal with a slight increase in maturation could be explained by kinetic effects in thermal cracking of kerogen with a low proportion of branched chains. As isomeric groups were rapidly exhausted, propane generation pathway rapidly changed and primary kinetic isotope effect completely shifted from central carbon position to terminal carbon positions in propane. These changes increased carbon isotope fractionation at terminal carbon positions, thereby reducing δ13Cterminal values and shifting δ13Ccentral < δ13Cterminal to δ13Ccentral > δ13Cterminal within a small maturity range. This work demonstrated that position-specific isotope distribution of propane can be applied to elucidate the chemical structure of kerogen.

The base metal sulfide and Ni–Co arsenide-bearing veins of Valsassina, Lombardy, Italy: a preliminary study

Abstract Valsassina (Lombardy, Northern Italy) is located in the Lombard Southern Alps and is characterised by the presence of a metamorphic basement, by a major late Variscan intrusive complex and by Carboniferous–Permian volcano-sedimentary cover units. These rocks host a pervasive system of inadequately studied mineralised veins. These veins are characterised by base metal (Pb, Zn, Cu and Fe) and complex polymetallic assemblages. In this study, we have investigated the ore textures, mineral compositions of sulfides and sulfosalts (by EMPA–WDS and LA–ICP–MS analyses), and stable isotopes (C and O) in carbonate gangue minerals of various mineralised veins to determine the conditions of deposition of these ore deposits. Two different vein families can be recognised in Valsassina: NNW–SSE veins characterised by a complex polymetallic sulfide–sulfosalt assemblage, also with Ni–Co–Fe arsenides and other Ag–Bi-bearing minerals; and NE–SW veins with a simpler, base metal sulfide assemblage. The Ni–Co-bearing NNW–SSE veins have some distinctive features of the ‘five-element vein’ type deposits, with the Ni–Co–Fe arsenide ore stage pre-dating a sulfide-tetrahedrite-dominated ore stage. LA–ICP–MS data for pyrite and sphalerite, and stable isotopic compositions (C and O) of the carbonate gangue minerals, show no clear differences between the two families of veins, which are probably linked genetically. The isotopic compositions of the Valsassina vein carbonates are closely comparable with the signature of several major five-element ore districts. Preliminary temperature estimates for the Valsassina vein systems were based on the sphalerite composition, applying the GGIMFis geothermometer. The estimated temperatures for the sulfide-dominated ore stage post-dating the Ni–Co minerals precipitation range between 100 and 250°C. The crosscutting relationships, observed for all the veins with the host rocks, suggest a possible late to post Variscan (late Permian) age, making these vein systems comparable with other late–post Variscan polyphase hydrothermal events affecting large sectors of the Southern Alpine domain.

The Dynamic Evolution Model of the Chemical and Carbon Isotopic Composition of C1-3 during the Hydrocarbon Generation Process.

A new approach is presented in this paper for the dynamic modeling of the chemical and isotopic evolution of C1-3 during the hydrocarbon generation process. Based on systematic data obtained from published papers for the pyrolysis of various hydrocarbon sources (type I kerogen/source rock, type II kerogen/source rock, type III kerogen/source rock, crude oil, and asphalt, etc.), the empirical evolution framework of the chemical and isotopic composition of C1-3 during the hydrocarbon generation process was built. Although the empirical framework was built only by fitting a large amount of pyrolysis data, the chemical and isotopic composition of C1-3 derived from the pyrolysis experiments all follow evolution laws, convincing us that it is applicable to the thermal evolution process of various hydrocarbon sources. Based on the simplified formula of the isotopic composition of mixed natural gas at different maturities (δ13Cmixed), δ13Cmixed = X×niA×δ13CiA+Y×niB×δ13CiBX×niA+Y×niB, it can be derived that the cumulative isotopic composition of alkane generated in a certain maturity interval can be expressed by the integral of the product of the instantaneous isotopic composition and instantaneous yield at a certain maturity point, and then divided by the cumulative yield of alkane generated in the corresponding maturity interval. Thus, the cumulative isotopic composition (A(X)), cumulative yield (B(X)), instantaneous isotope (C(X)), and instantaneous yield (D(x)) in the dynamic model, comply with the following formula during the maturity interval of (X0~X). A(X) = ∫X0XCX×DXdxB(X), where A(X) and B(X) can be obtained by the fitting of pyrolysis data, and D(x) can also be obtained from the derivation of B(X). The dynamic model was applied on the pyrolysis data of Pingliang Shale to illustrate the quantitative evolution of the cumulative yield, instantaneous yield, cumulative isotope, and instantaneous isotope of C1-3 with increasing maturity. The dynamic model can quantify the yield of methane, ethane, and propane, as well as δ13C1, δ13C2, and δ13C3, respectively, during the hydrocarbon generation process. This model is of great significance for evaluating the natural gas resources of hydrocarbon source rock of different maturities and for identifying the origin and evolutionary process of hydrocarbons by chemical and isotopic data. Moreover, this model provides an approach to study the dynamic evolution of the isotope series of C1-3 (including reversed isotopic series), which is promising for revealing the mechanism responsible for isotopic reversal when combined with post-generation studies.

Shallow carbonate geochemistry in the Bahamas since the last interglacial period

The carbon isotope composition (δ13C) of ancient shallow-water carbonates frequently is used to reconstruct changes to Earth's global carbon cycle and to perform chemostratigraphic correlation. However, previous work demonstrates that local banktop processes also exert an important control on shallow carbonate δ13C as well as other isotope systems like δ18O. To effectively interpret ancient δ13C records, we must understand how both global carbon cycle perturbations and changes to local conditions are translated to the stratigraphic record. Modern environments, while imperfect analogues, can serve as a guide for interpreting physical and geochemical records of more ancient environments. Shallow carbonate strata from the most recent Pleistocene glacial cycles, which drove high-amplitude perturbations to sea level, temperature, and pCO2 without significantly altering the δ13C of global-mean seawater DIC, present an opportunity to begin untangling signals of global and local processes. However, the geochemistry of Pleistocene platform carbonates largely was overprinted by dissolution and meteoric diagenesis during glacial sea level lowstands. To understand how shallow carbonate geochemistry has changed during the Pleistocene, we instead look to the periplatformal slope and proximal basins. These deep environments serve as a refuge for carbonate produced on the shelf and exported to the slope, and contain a record of shallow carbonate geochemistry that persists across glacial cycles. We study 21 short piston cores from around Bahamian platforms to quantify differences in banktop production and geochemistry between the Holocene interglacial, the last glacial period, and the last interglacial (LIG) period. We show that mud production persists on the periplatformal slopes during the last glacial period, but differences in geochemistry between glacial and interglacial carbonates are a complex function of surface conditions and diagenesis. In contrast, Holocene and LIG carbonates show no evidence of post-depositional alteration, and offer the chance to study differences in δ13C and δ18O between interglacials. We find that while the δ13C of aragonite mud is the same during the Holocene and LIG, the LIG carbonate factory may have delivered more aragonite mud to the periplatform. In addition, the mean δ18O of this mud is elevated compared to the Holocene. We posit that these differences are caused by changes to regional climate and LIG surface conditions.