Carbon Isotopic Composition Research Articles

Experimental assessment of elemental analyzer isotope ratio mass spectrometry normalization methodologies for environmental stable isotopes.

In stable isotope mass spectrometry, isotope delta values are normalized to internationally recognized reference scales using a combination of certified and in-house isotope reference materials. Numerous techniques exist for performing this normalization, but these methodologies need to be experimentally assessed to compare their effect on reproducibility of isotope results. We tested normalization methods by the number of reference materials used, their matrix, their isotope range, and whether normalization required extrapolating beyond the isotope range. We analyzed eight commercially available isotope reference materials on a ThermoFinnigan Delta-V isotope ratio mass spectrometer (IRMS) and an Elementar VisION IRMS for nitrogen and carbon isotope composition via solid combustion with an elemental analyzer and computed every possible isotope normalization (n = 612). Additionally, we assessed how sample matrix affected linearity effects on both instruments using five in-house reference materials. Normalizations exhibited the best performance when the reference materials spanning an isotope range of at least 20‰ were matrix matched with the samples and did not require extrapolation beyond the calibration curve. When these conditions were not met, the number of reference materials used had a significant effect on accuracy, with normalizations composed of two reference materials exhibiting particularly inconsistent performance at isotope ranges below 20‰. Linearity effects were found to exceed instrument precision by two orders of magnitude irrespective of matrix type and were not predicted by working gas diagnostics. Interlaboratory comparability of isotope results is improved when operators of elemental analyzer isotope ratio mass spectrometry (EAIRMS) systems select reference materials spanning an isotope range of at least 20‰. Additionally, using three or more isotopic reference materials, avoiding extrapolation beyond the range of the normalization curve, and matching the matrix of the reference materials to the samples improve normalizations.

GEOCHEMISTRY OF OILS AND GASES FROM THE VERKHNECHONSKOYE FIELD, EAST SIBERIAN BASIN: APPLICATION OF ANALYTICAL RESULTS TO RESERVOIR CHARACTERISATION

A geochemical study was carried out on oil and gas samples from the Verkhnechonskoye field, located on the Nepa‐Botuoba Anteclise in the central‐southern part of the Siberian Platform. The goal of the study was to distinguish between fluids derived from the V10‐13 and B12 reservoir units in the Vendian (Neoproterozoic) Katanga and Nepa Formations and to identify the producing reservoir using geochemical data. The results of analyses of 12 oil and 13 associated gas samples from the two reservoirs showed that all the fluids have similar geochemical properties including: low Pr/Ph ratios (0.78‐1.00); a predominance of C29 over C27 and C28 steranes; a predominance of odd‐numbered C21‐C25 n‐alkylbenzenes over their even‐numbered homologues; the presence of 12‐ and 13‐methylalkanes; and a high relative abundance of tricyclic terpanes (cheilantanes). All these properties are consistent with those of the properties of petroleum from other fields on the Siberian Platform. The molecular and stable carbon isotope compositions of the oils and gases suggest that they were derived from marine organic matter with a high algal input deposited under reducing conditions. To date, specific source rocks which generated the oil and gas present at fields on the Nepa‐Botuaoba Anteclise have not conclusively been identified, but potential candidates include the Upper Riphean Iremeken and Ayan Formations and more probably the Vendian Zherbinskaya, Seralakh, Vanavara and Nepa Formations.The second part of the study demonstrates the application to reservoir geochemistry of C3‐ and C4‐ alkylbenzene compounds together with more conventional biomarkers. Key parameters were selected using statistical processing and displayed in graphic profiles. These profiles allowed the oil and gas samples to be classified according to the reservoir from which they were derived based on their geochemical properties. Parameters based on C3‐ and C4‐ alkylbenzene compounds were most effective in discriminating between oils from the two reservoirs. In addition, a new parameter is proposed based on the contents of 1‐methyl‐3‐isopropylbenzene, 1‐methyl‐2‐isopropylbenzene and 1‐methyl‐2‐propylbenzene; this parameter correlates closely with the pristane/phytane ratio and can be used as an additional indicator of the level of oxicity in the source rock depositional environment.

Characteristics of methane and carbon dioxide in ice caves at a high-mountain glacier of China

The exploration of the spatiotemporal distribution of greenhouse gas (GHG) exchange in the cryosphere (including ice sheet, glaciers, and permafrost) is important for understanding its future feedback to the atmosphere. Mountain glaciers and ice sheets may be potential sources of GHG emissions, but the magnitude and distribution of GHG emissions from glaciers and ice sheets remain unclear because observation data are lacking. In this study, in situ CH4 and CO2 and the mixing ratios of their carbon isotope signatures in the air inside an ice cave were measured, and CH4 and CO2 exchange in the meltwater of Laohugou glacier No. 12, a high-mountain glacier in an arid region of western China, was also analyzed and compared with the exchange in downstream rivers and a reservoir. The results indicated elevated CH4 mixing ratios (up to 5.7 ppm) and depleted CO2 (down to 168 ppm) in the ice cave, compared to ambient levels during field observations. The CH4 and CO2 fluxes in surface meltwater of the glacier were extremely low compared with their fluxes in rivers from the Tibetan Plateau (TP). CH4 and CO2 mixing ratios in the air inside the ice cave were mainly controlled by local meteorological conditions (air temperature, wind speed and direction) and meltwater runoff. The carbon isotopic compositions of CH4 and CO2 in the ice cave and terminus meltwater indicated δ13C-CH4 depletion compared to ambient air, suggesting an acetate fermentation pathway. The abundances of key genes for methanogenic archaea/genes encoding methyl coenzyme M reductase further indicated the production of CH4 by methanogenic archaea from the subglacial meltwater of high-mountain glaciers. The discovery of CH4 emissions from even small high-mountain glaciers indicates a more prevalent characteristic of glaciers to produce and release CH4 from the subglacial environment than previously believed. Nevertheless, further research is required to understand the relationship between this phenomenon and glacial dynamics in the third pole.

Geochemical and palynological characteristics of the Maykop sections in the north-west of the Shamakha-Gobustan region (Azerbaijan)

The article provides a comparative analysis of the results of complex palynological and geochemical studies of rocks from natural outcrops of Lagich, Angekharan and Agsu in the north-west of the Shamakhi-Gobustan region. A comparison of the distribution features of palynomorph species with the lithofacies variability of sediments made it possible to reveal the conditions of sedimentation during the formation of the described sections. In addition, the age of the units identified in the Maikop deposits in Lagich and Angekharan was clarified by analogy with the formations and horizons of similar ages in the Western and Central Ciscaucasia. The boundary of Eocene and Oligocene deposits in the Lagich section is assumed to be in the interval of 80–115 m. Late Eocene deposits occurring at the base of the section are apparently an analogue of the boundary deposits of the Beloglinskaya and Pshekhskaya formations of the Ciscaucasia. The presence of cold-water dinocysts of the species I.recurvus and calcareous nannofossils Coccolithus pelagicus in the boundary interval corresponds to the existing ideas about climate cooling at the end of the Eocene - beginning of the Oligocene. The formation of sediments in the upper intervals of the section probably occurred in more open marine conditions, relatively warm water, but with low levels of nutrients (nitrates). This interval of sediments with a characteristic phytoplankton complex can be correlated with the middle part of the Khadum horizon, an analogue of the Nizhny Morozkinsky subformation and, possibly, with the upper clayey part of the Polbinsky formation of Western and Central Ciscaucasia. The accumulation of the lower units of the studied part in the Angekharan, dated to the Early Oligocene, most likely occurred in a marine, shallower environment with possible short-term transgressive impulses. Overall, it is possible to suggest a proximal environment of high nutrient content in well-mixed waters within the inner neritic zone. An analogue of the deposits of this interval can be the Lower Morozkinsky Formation and the lower parts of the Upper Morozkinsky Formation of the Ciscaucasia. The significant increase in deflandroids in the upper part of the Angekharan section is similar to the changes noted during the transition to the zone of Deflandrea spinulosa f. Majkopica in the upper part of the Batalpashinskaya Formation of the late Oligocene in Ciscaucasia. The accumulation of sediments probably occurred in a marine basin with signs of stagnation in brackish, eutrophic environment, with a short-term supply of material from the photic zone. The conclusions about the peculiarities of changes in the depositional conditions in the study area are also confirmed by the results of geochemical studies. The deposits of the studied sections are represented by both terrestrial and aquatic types of organic matter (OM). Terrigenous OM was more typical in rocks from the Lagich and Agsu outcrops. The OM of rocks from the Lagich section varies from marginally mature to mature. In the Angekharan section the OM is thermally immature, as evidenced by the low Tmax values. Despite the small thickness of the Agsu outcrop, rock samples from this section contain kerogen of various stages of transformation from immature to mature. The carbon isotope composition (CIC) of Corg in sediments within the studied sections is in the δ13C range, characteristic of Oligocene sediments in the Paratethys. There is a higher enrichment of the 13C isotope in OM in sediments from the Agsu section.

Can species climate niche predict canopy growth, functional traits and phenotypic plasticity in urban trees?

There is much uncertainty in how climate change will impact the performance of urban trees. Climate niche modelling predicts that many urban tree species may become unsuitable in future climates, but this has rarely been tested in cities. Broad planting of diverse tree species in different cities provides the opportunity to test climate niche predictions. Here we investigated if the climate of origin of 14 urban tree species influenced tree growth, trait expression, and phenotypic plasticity. We determined climate niche limits for all species and measured canopy growth rates of individual trees from 2013 to 2021 in the two largest Australian cities: subtropical Sydney, and temperate Melbourne. Six functional traits including leaf water potential at turgor loss point (TLP), wood density (WD), leaf dry matter content (LDMC), specific leaf area (SLA), carbon isotope composition (δ13C) and Huber value (HV) were measured in both cities. Trees planted outside their climate niche limits had lower growth than trees planted inside their climate niche in the temperate but not subtropical city. Species with lower MAP of origin (i.e., drier) had faster canopy growth in both cities. Species with low MAP and high heat moisture index (HMI) at their origin had more negative TLP and greater WD, indicating species from drier environments maintain their high drought tolerance in cities. Trees planted in drier Melbourne had more negative TLP, higher WD and higher LDMC than in Sydney, demonstrating phenotypic plasticity in urban trees. Wetter origin species showed greater phenotypic plasticity in TLP, WD and δ13C. Canopy RGR was negatively related with δ13C reflecting a strong impact of stomatal behaviour on urban tree growth. Our study provides limited support that species climate niche limits reliably predict urban tree growth, so we caution against solely using climate niche matching and advocate for inclusion of functional traits when selecting urban tree species.

Re-determination of R(13C/12C) for Vienna Peedee belemnite (VPDB).

The isotope ratio for the internationally agreed but virtual zero-point of the carbon isotope-delta scale, Vienna Peedee belemnite (VPDB), plays a critical role in linking carbon isotope delta values to the SI. It is also a quantity used for various data processing procedures including '17O correction', clumped isotope analysis and conversion of carbon isotope delta values into other expressions of isotopic composition. A value for RVPDB(13C/12C) with small uncertainty is therefore desirable to facilitate these procedures. The value of RVPDB(13C/12C) was determined by errors-in-variables regression of isotope delta values traceable to VPDB measured by isotope ratio mass spectrometry against isotope ratios traceable to the SI by use of gravimetric mixtures of 12C- and 13C-enriched d-glucose measured by multicollector inductively coupled plasma mass spectrometry. A value of RVPDB(13C/12C) = 0.0111105 ± 0.0000042 (expanded uncertainty, k = 2) was obtained. The new value for RVPDB(13C/12C) agrees very well with the consensus values calculated from previous measurement results proposed by Kaiser and by ourselves, as well as recent determinations independent of mass spectrometry. The expanded uncertainty of 0.4‰ when expressed as an isotope delta value is a tenfold improvement over the previous best measurement of the isotopic composition of carbon.

Origins of authigenic gypsums and carbonate minerals in sediments at a cold seep site in the Sea of Marmara

In the Western High of the Sea of Marmara, where pervasive gas hydrate and hydrocarbon gas seepage occurs, late Pleistocene-Holocene sediments are composed of a lower lacustrine and an upper marine unit. The sedimentary evolution, gypsum formation and carbonate anomaly, under the complex sedimentary environment at cold seep sites on the Western High, have not been systematically well explained. The transition from the lacustrine to marine unit occurs at around 7.5 m below the sea floor (mbsf), with a sulfidization front present in the lacustrine sediments just below it, and the marine unit includes a sapropel layer between 5.20 and 7.20 mbsf. The sedimentary sequence is characterized by authigenic minerals including pyrite, carbonates, and gypsum in the upper 0.50 mbsf, corresponding to the present-day sulfate-methane transition zone (SMTZ) near the seafloor. Mineralogical, chemical and isotopic compositions (13C, 18O, 34S, 26Mg) of the sediments in the core studied show their close relationship with intensive sulfate-driven anaerobic oxidation of methane (AOM) and other hydrocarbons. The dissolution of carbonate, related to the gas and oil migration, and organic matter enrichment might be the main cause of carbonate deficiency in the sapropel unit. Heavy carbon isotopic composition (δ13CCarb = 6.98‰) of carbonate at 4.30 mbsf implies that the carbon might be the residual by-product of subsurface biodegradation of seeping petroleum. The formation of secondary gypsum and partial dissolution of carbonate in the Sea of Marmara is commonly considered of being associated with the aerobic oxidation of pyrite. However, the euhedral authigenic gypsum studied might be with different origins, possibly including anaerobic oxidation of Fe-sulfides, carbonate deficiency in the sapropel unit and AOM. Gypsums below SMTZ are with the size of hundreds of microns. Linear pits and grooves are developed on these gypsum surfaces, probably due to corrosion by the methane-rich fluid of latest hydrocarbon seepage. Platy hexagonal gypsum in SMTZ, without any corrosion on crystal surface, might be associated with the changing flux of the acidic composition (e.g. CO2) in the seepage. Depleted-26Mg by about 1‰ in the SMTZ might be caused by the upward seepage of hydrocarbons. Magnesium isotope of authigenic carbonate could be a valid proxy for the recognition of SMTZ in a hydrate geo-system.

Isotopic composition of carbon (δ13C) and nitrogen (δ15N) of petrologically different Tertiary lignites and coals

This study investigates the carbon (δ13Corg) and nitrogen (δ15N) isotopic composition of tertiary lignites and coals from six sedimentary basins: Velenje, Mura-Zala, and Zasavje in Slovenia; Sokolov in Czech Republic, Barito in Indonesia; and Istria in Croatia. The aim is to investigate the correlation between the fine detrital (fD) component and δ13C and δ15N in Velenje lignite samples. Additionally, we aim to evaluate the biogeochemical processes of organic substances during their deposition in all analyzed samples, calculate their δ13CCO2 values and compare the analyzed values of δ13C and δ15N to those reported in the literature. Thirty-two samples were analyzed, predominantly from the Velenje ortho-lignite (Pliocene), with additional lignites and coals from the Pannonian to Paleocene epochs for comparison. Carbon isotopic composition (δ13Corg) ranged from -27.9 to -23.6 ‰, and nitrogen isotopic composition (δ15N) ranged from 1.8 to 7.4 ‰. The fine-detrital lithotypes of the Velenje ortho-lignite exhibited the most negative δ13Corg values due to anaerobic bacterial activity in an intramontane alkaline lake environment influenced by the carbonate hinterland. Moreover, gelification processes affected fine-detrital organic matter more than larger wooden pieces. Terbegovci, Hrastnik meta-lignites, and Barito sub-bituminous coal also displayed low δ13Corg values, indicating limited gelification, while variations in the δ15N values suggested differences in mineralization. The Velenje xylitic lithotypes have higher δ15N values, indicating a more intense mineralization under aerobic conditions. Raša ortho-bituminous coal, deposited in a brackish environment, displayed the highest δ13Corg values and a wide range of δ15N values due to fluctuating water tables in a paralic carbonate platform environment. The lowest δ15N value was observed in the Sokolov Basin lignite coal, indicating minimal mineralization and low bacterial activity. The isotopic composition of CO2 in air (δ13Cair), which was calculated using the δ13C values in lignites and coal, ranged from -8.4 to -3.4 ‰, with Velenje lignite displaying the minimum value and Raša coal showing the maximum value. The determined δ13C and δ15N values of the coal and lignite samples in this research fall within the typical range of world coals.

Geochemical and Organic Petrological Characteristics of the Bituminous Carbonate Succession (Upper Cretaceous Shu'ayb Formation) in Northern Jordan: Implications for Organic Matter Input and Paleosalinity, Paleoredox, and Paleoclimatic Conditions.

Bituminous carbonate rocks of the Upper Cretaceous Shu'ayb Formation from the Ajloun outcrop in Northern Jordan were geochemically and petrologically analyzed in this study. This study integrates kerogen microscopy results with geochemical results (i.e., biomarker, stable carbon isotope, and major elemental compositions) to understand the organic matter (OM) inputs and to reveal the dispositional setting and its effect on the occurrence of OM. The Shu'ayb bituminous carbonate rocks have high total organic carbon (TOC) and sulfur (S) contents, with average values of 12.3 and 4.59 wt %, respectively, indicating redox conditions during their precipitation. The high abundance of alginite (i.e., lamalginite) in the Shu'ayb bituminous carbonate sediments is a further evidence for redox conditions. The finding of mainly marine-derived OM was also demonstrated by the biomarker distribution and carbon isotope composition. The biomarkers are represented by a narrow Pr/Ph ratio of up to 0.97, abundance of tricyclic terpanes, and high C27 regular sterane, indicating that the OM was primarily derived from phytoplankton algae, along with small amounts of land plant-derived materials, and were accumulated under reducing conditions. The studied Shu'ayb bituminous carbonate facies is composed of mainly calcium (CaO; average, 45.10 wt %), with significant amounts of silicon (Si2O3; avg., 9.35 wt %), aluminum (Al2O3; avg., 6.91 wt %), and phosphorus (P2O3; avg., 1.47 wt %) and low amounts of iron (Fe2O3) and titanium (TiO2) of less than 1 wt %, indicating that the detrital influx was low in an open water depth system with higher primary bioproductivity. The geochemical proxy suggests that the Shu'ayb bituminous carbonate facies was established in a saline water environment, with Ca/Ca + Fe and S/TOC values of more than 0.9 and 0.50, respectively, which could be attributed to the increase in reducing conditions of the water column. The chemical index of alteration values of more than 0.8 also indicate that the Shu'ayb bituminous carbonate facies formed during warm and humid climatic conditions, thereby resulting in intense subaerial weathering.

An algorithm-guided Ediacaran global composite δ13Ccarb–Bayesian age model

While it remains uncertain whether excursions in the stable carbon isotopic composition of Ediacaran marine carbonate (δ13Ccarb) represent globally synchronous events (or a direct measure of ocean carbon cycling), the absence of widely distributed and readily preservable fauna, and the presence of several iconic carbon isotope excursions (CIEs), has sustained δ13Ccarb correlation as the primary means to establish relative time relationships for Ediacaran successions. Here we present an Ediacaran global δ13Ccarb composite built with a dynamic time warping (DTW) time-normalization algorithm that generates libraries of least-squares alignments between chemostratigraphic records of unequal length and distinct sediment accumulation rates. When developing a δ13Ccarb composite for each of 16 globally distributed Ediacaran paleo-depositional regions, we selected high Pearson r alignments that conformed with published geological guidance about the correlation of constituent sections. When applying DTW to align these regional algorithmic composites into one global δ13Ccarb stack, we selected alignments that allied the excursions that field workers have established (or speculated) are the Marinoan cap carbonate excursion, the Shuram excursion, and/or the basal Cambrian excursion. There are strengths and weaknesses to making explicit the temporal relationships (point-to-point correspondences) often left implicit in visual correlation. One strength is to extrapolate depositional ages by means of isotopic correlation, and here we explored this with a Bayesian Markov chain Monte Carlo age model that predicts a median age, and uncertainty, for every carbonate stratum in the global Ediacaran δ13Ccarb composite. Yet, one must caution against a false accuracy that can arise from selecting one alignment among many possibilities––the likelihood that time-uncertain time series can be stretched and squeezed into one unequivocal alignment is low. Thus, while these alignments are grounded in the expert assessment of the field worker, this global Ediacaran δ13Ccarb–Bayesian age model should be viewed as a working hypothesis to enrich, but not arbitrate, discussions of the correlation, synchrony, and completeness of Ediacaran successions.

The Rare Earth Element Distribution in Marine Carbonates as a Potential Proxy for Seawater pH on Early Earth

Understanding the marine environment of early Earth is crucial for understanding the evolution of climate and early life. However, the master variable of Archean and Proterozoic seawater, the pH, is poorly constrained, and published ideas about the pH range encompass ~7 pH units from mildly acidic to hyperalkaline. To better infer ancient seawater pH, we examine the possibility of a seawater pH proxy using rare earth elements (REEs) in marine carbonates. The principle is based on increasing concentrations of heavy rare earth elements in solution relative to the light REEs with decreasing pH due to REE complexation and scavenging. We calibrated such an REE pH proxy using pH variability in modern seawater and tested the proxy with ~100 REE measurements from 13 separate carbonate formations. We compared our pH estimates derived from the REE proxy to published pH estimates of Cenozoic and Neoproterozoic seawater that use the established pH proxy of boron isotopes (δ11B). REE-pH estimates agree with the Cenozoic and the Ediacaran δ11B-pH proxy based on the type of carbonate and boron isotopic composition at corresponding times. The uncertainty in our REE-pH proxy can probably be explained by model assumptions, noise from freshwater influence, siliciclastic input, and diagenesis. This proof-of-concept study demonstrates that the REE-pH method provides pH estimates comparable to boron isotope pH estimates within uncertainties, which potentially could constrain changes in Precambrian seawater pH to better understand the coevolution of life and early Earth’s environment.

Generation of abnormal distributions of inter- and intramolecular δ13C compositions in hydrocarbons from gold tube pyrolysis of an Australian torbanite

Abnormal stable carbon isotopic (δ13C) compositions, deviating from the conventional order of δ13C1 < δ13C2 < δ13C3, are frequently observed in natural gas reservoirs. For thermogenic gas, these anomalies, such as δ13C1 < δ13C3 < δ13C2 or δ13C1 > δ13C2 > δ13C3, have multiple formation mechanisms including gas mixing in conventional systems and desorption processes of gaseous hydrocarbons in unconventional shale gas systems due to their inconsistency with Rayleigh fractionation processes. Considering distinct reaction pathways (e.g., C1 polymerized to C2), these aberrant δ13C signatures are often construed as intrinsic hallmarks of extensively evolved natural gas. However, on the basis of gas generation simulation, not all findings exhibit abnormal δ13C values, hinting at multifaceted and intricate mechanisms governing the isotopic fractionation of alkane gas components. This study conducted gold tube pyrolysis of an Australian torbanite, revealing four distinct types of δ13C anomalies in hydrocarbon classes. Polycyclic aromatic hydrocarbons (PAHs) exhibited δ13C values more negative than co-occurring n-alkanes. δ13C3 displayed a negative trend shift from EasyRo = 3.5 %, resulting in a partially δ13C-reversed gas (δ13C1 < δ13C3 < δ13C2) formed at EasyRo ≈ 4.1 %. Moreover, intramolecular δ13C3 (both terminal and central carbons, termed δ13Ca and δ13Cb, respectively) reversed alongside the overall δ13C3 trend. Additionally, the evolution of site preference in δ13C3 (termed ‰SP = δ13Ca – δ13Cb) transitioned from progressively negative to positive. The results of this study demonstrate that the potential conversion between saturated hydrocarbons, aromatic hydrocarbons, and alkane gases is at least partially responsible for δ13C anomalies, but also that gaseous hydrocarbons formed from other fractions at high maturity cannot be ruled out, such as kerogen and pyrobitumen.

Milk production in pottery. Evidence for various exploited resources used by the first farmers in Central Pyrenees using the morphological, chemical and stable carbon isotopic composition of organic residues from ceramic vessels

Milk production in pottery. Evidence for various exploited resources used by the first farmers in Central Pyrenees using the morphological, chemical and stable carbon isotopic composition of organic residues from ceramic vessels

Paleoclimatic and paleogeographic significance of the early Santonian ice-rafted dropstones in the Songliao Basin, NE China

Two ice-rafted dropstones were discovered in the Yaojia Formation (early Santonian) of wells Ao14 and F247 in the Songliao Basin, northeastern China. The dropstone from well Ao14 was further studied using computed tomography (CT) scanning, sporopollen, carbon and oxygen isotope, and zircon U–Pb isotope analyses. The results show that the dropstone is composed of quartz monzonite and has an age of 178.0 ± 3.3 Ma. Based on the bedrock age analysis around the Songliao Basin, it is suggested that the dropstone in well Ao14 may have originated from the Zhangguangcai Range. The palynoflora assemblage indicates a mixed survival of cold and warm palynomorphs. The carbon and oxygen isotope compositions of the synsedimentary calcareous clasts surrounding the dropstone exhibit obvious negative biases, suggesting that glacier meltwater flowed into the paleo-lake, probably due to the significant topographic height difference between the Songliao Basin and adjacent areas during the early Santonian. Additionally, it can be inferred that coastal mountains formed in the Zhangguangcai Range area, which is located southeast of the Songliao Basin, and the dropstones derived from this region. During the cold season, the dropstones may be transported to the edge of Songliao Lake by avalanche and mixed with carbonate debris. As the seasons changed, the lake ice broke into pieces and carrying the dropstones and carbonate debris into the deep lake area. The present research provides direct evidence of a brief global cold event and the presence of high mountains in the southeastern Songliao Basin during the early Santonian in the Cretaceous greenhouse world.

Geochemistry of oils and condensates from the lower Eagle Ford formation, south Texas. Part 6: Carbon isotopes

Compound specific carbon isotope analyses were performed on a well-characterized suite of unconventional oils and condensates produced from the lower Eagle Ford Formation. Thermal maturity is the major influence on the δ13C values of C3–C19 hydrocarbons. From ∼0.8 to ∼1.1 %Ro, the main stage of oil generation, the δ13C values of most measured hydrocarbons remain relatively constant: n-alkanes are ∼ −30 ‰: light aromatic hydrocarbons, cycloalkanes and isoprenoids are ∼ −29 to −28 ‰. Only the C4 to C10 methylalkanes exhibit high variance with carbon number with δ13C values ranging from ∼ −32 to −28 ‰, respectively. Hydrocarbons from samples ∼1.1 to 1.3 %Ro, the late oil generation stage, are 13C-enriched by ∼1–∼2 ‰. This is the range typically assigned to the influence of thermal maturity on oil from many conventional petroleum systems. The onset of significant oil cracking occurs at ∼1.3 %Ro and all measured hydrocarbons systematically become progressively 13C-enriched although the degree varies by compound class and carbon number. The δ13C values of individual hydrocarbons shift by as much as ∼ +9 ‰ for propane and butane to only ∼ +3 ‰ for methylcyclopentane from <1.1 to 1.7 %Ro. The 13C-enrichments observed in the Eagle Ford oils/condensates with increasing maturity are attributed to the kinetic isotope effect (KIE), whereby 12C–12C bonds cleave faster than 12C–13C bonds. No evidence for isotopic equilibrium was found. The consistency of the sums of the weighted δ13C values for C4–C7n-alkane/methylalkane isomers provides support for Mango's (2000a) theory that these hydrocarbons are generated from precursors with a common chemical structure that pass through a similar transition state.Source facies exert only a minor influence on the carbon isotopic composition of Eagle Ford oils/condensates. Small variances in the 13C values of C6+n-alkanes, cyclohexane and methylcyclohexane are consistent with oils produced east of the San Marco Arch being generated from shales with a higher influx of terrestrial high plant matter compared to the shales west of the Arch. Phase fractionation was shown to have a measurable impact on the δ13C values of the most volatile hydrocarbons in evaporated samples and on the least volatile hydrocarbon that underwent phase separation in the subsurface during production.

Depositing skeletal remains in Czech and Moravian ossuaries and associated climatic variations

AbstractSamples of the bones of 47 individuals from 46 Czech and Moravian ossuaries were dated by the 14C method and analyzed for the collagen isotopic composition of carbon (δ13C) and nitrogen (δ15N). Most of the data for the ages of the remains corresponded to the cooler and damper periods described over the past 1000 years. Of the studied samples, the greatest number of remains corresponded to the Spörer (1400–1570), Dalton (1790–1830) and Wolf minima (1280–1350). One sample studied falls within the Maunder minimum (1645–1715). It can be assumed that these minima are connected with a reduced production of food and fodder, that may have initiated famines, epidemics and armed conflicts. Individual climatic minima showed positive correlations between δ13C and δ15N values, indicating that the individuals studied consumed complementary plant or animal diets to different degrees. The elevated δ15N values in our studied samples compared to the skeletal compositions of the population of the La Tène period (380 – 150 BC) and Germanic inhabitants in the territory of Bohemia (5th–6th centuries AD) and Great Moravia (9th–early 10th centuries AD) might reflect the effect of greater consumption of animal proteins or the proteins of omnivorous animals and fish, which compensated for the lack of plant foodstuffs during the colder periods.The isotopic composition of carbon and nitrogen of the bone collagen for the Spörer and Dalton minima differs from the Wolf minimum. The younger minima show higher δ15N values for a given δ13C value.

Natural gas exploration potential and favorable targets of Permian Fengcheng Formation in the western Central Depression of Junggar Basin, NW China

Based on the organic geochemical data and the molecular and stable carbon isotopic compositions of natural gas of the Lower Permian Fengcheng Formation in the western Central Depression of Junggar Basin, combined with sedimentary environment analysis and hydrocarbon-generating simulation, the gas-generating potential of the Fengcheng source rock is evaluated, the distribution of large-scale effective source kitchen is described, the genetic types of natural gas are clarified, and four types of favorable exploration targets are selected. The results show that: (1) The Fengcheng Formation is a set of oil-prone source rocks, and the retained liquid hydrocarbon is conducive to late cracking into gas, with characteristics of high gas-generating potential and late accumulation; (2) The maximum thickness of Fengcheng source rock reaches 900 m. The source rock has entered the main gas-generating stage in Penyijingxi and Shawan sags, and the area with gas-generating intensity greater than 20×108 m3/km2 is approximately 6 500 km2. (3) Around the western Central Depression, highly mature oil-type gas with light carbon isotope composition was identified to be derived from the Fengcheng source rocks mainly, while the rest was coal-derived gas from the Carboniferous source rock; (4) Four types of favorable exploration targets with exploration potential were developed in the western Central Depression which are structural traps neighboring to the source, stratigraphic traps neighboring to the source, shale-gas type within the source, and structural traps within the source. Great attention should be paid to these targets.

Late Mesoproterozoic iron and manganese deposition on a deep-water carbonate platform (Penganga Group), Adilabad, India: Constraints from C, O and Sr isotopes

Abstract The Penganga Group in the Pranhita-Godavari Rift Valley of central India includes a rather unique example of Late Mesoproterozoic iron and manganese formations deposited in a deep-water below storm wave base distal carbonate platform environment. The carbonate rocks of the Penganga Group are mostly lime-mudstones that have been classified into a number of sedimentary cycles with intervals mostly distinguished by color, ranging from brown/pink and siliceous gray to steel-gray and black. At least two about one-meter-thick Mn-Fe formations occur in siliceous gray limestone of the distally steepened part of the Penganga carbonate platform. A number of northwest-southeast striking thrust faults repeat the succession in down dip sections bringing up distal profiles of the Penganga Group against proximal counterparts at the present exposure level. This contribution provides the first comprehensive record of stable C and O and radiogenic Sr isotopes for proximal and distal profiles, allowing for direct comparison and thus, providing context for the environmental conditions of Fe and Mn deposition in a Mesoproterozoic platform environment. Carbon and oxygen isotope compositions determined from the proximal and distal profiles of the platform yield trends that are attributed to variations in circulation pattern and cycles of warm and cold climatic stages across the platform. Secular trends of Sr-isotope compositions suggest a variation in continental input between cold (0.7065) and warm climatic stages (0.7149), similar to that observed for modern marine sediments. The sedimentation of siliceous deposits and ferromanganese deposits in the distal platform environment was likely favored by the onset of upwelling circulation during cold climatic stages. The moderately negative δ13CPDB values (-5.34‰ to -6.34‰) of the Mn-carbonates and variation in δ13Corg values 31.7‰ to -21.7‰ obtained for early diagenetic Mn-carbonate ovoids indicate oxidation of organic matter in the ferromanganese deposits by Mn-oxides during early diagenesis. We conclude that upwelling and platform-wide deposition of ferromanganese deposits on the Penganga carbonate platform may mark the transition from the stagnant Mid-Proterozoic ‘sulphidic’ ocean to a ‘respiring’ open ocean during the Late Mesoproterozoic Era.

Spring buds of European woody plants have old 14C age

Trees and shrubs maintain carbon reserves to support their functions during periods when metabolic demand exceeds carbon supply, such as during the dormant season. To gain a better understanding of carbon storage and utilisation dynamics of eight woody plant species in temperate Central Europe, bud scale and leaf samples were collected to determine the radiocarbon age of fresh sprouts in trees and shrubs, at three background sites avoiding local emissions that may influence affect the observed 14C/12C ratio. The accelerator mass spectrometry-based bomb-radiocarbon approach, to determine the age of the mobilized carbon in the plant bud samples from storage, was complemented by stable carbon isotope measurements. The bomb-radiocarbon dating technique was used to determine the age of the samples, while a northern hemispheric atmosphere 14CO2 dataset was used to calibrate the radiocarbon ages of the plant samples. The youngest observed calibrated radiocarbon age of the buds was over 4 years, and the oldest was even 9 years old. There was no significant difference between the ages of bud scales and embryonal leaf laminas. Our results show that there is a considerable amount of stored older carbon in the woody stems that can be used to produce buds in spring, which is a complex mixture of stored carbon of different ages, but there is no relationship between the radiocarbon age and the stable carbon isotope composition. The observed results show that not only the tree species, but shrubs also can store and use significantly older carbon pools, the carbon storage intensity is similar for trees with trunks and short-stemmed shrubs branching directly above the ground, i.e. carbon storage starts in young twigs and continues in ageing branches.

High temperature and solar radiation in the Red Sea enhance the dissolution of crude oil from surface films

The Red Sea is a hotspot of biodiversity susceptible to oil pollution. Besides, it is one of the warmest seas on the Earth with highly transparent waters. In this study, we estimated the oil dissolution rates under natural sunlight spectra and temperature conditions using coastal oil slicks collected after the 2019 Sabiti oil spill in the Red Sea. Optical analyses revealed the significant interactive effect of sunlight and temperature in enhancing the dissolution of oil into dissolved organic matter (DOM). The highest oil dissolution rate (38.68 g C m−3 d−1) was observed in full-spectrum sunlight. Oil dissolution significantly enhanced total organic carbon (TOC) and polycyclic aromatic hydrocarbons (PAHs) in seawater. High nucleic acid (HNA) bacteria, likely the oil degraders, proliferated from 30 to 70 – 90% after 4 days. The heavier stable carbon isotopic composition of methane (δ13C-CH4) and lighter stable carbon isotopic composition of carbon dioxide (δ13C-CO2) indicate the putative role of bacterial processes in the natural degradation of crude oil. The results indicated that the combined effect of temperature and solar radiation enhanced the biological and photochemical dissolution of oil on the Red Sea surface.