Carbon Isotope Values Research Articles

Ediacaran cap carbonates with microbial build-ups capping barite-bearing methane seep networks in the Kaarta Mountains, Taoudeni Basin, Mali

Defining the variability and distribution of methane seeps and microbial activity in the aftermath of the Marinoan glaciation is a long-standing challenge in the field of Snowball models. Early diagenetic barite is commonly linked to tepee structures and associated breccias lacking microbial textures and fabrics, giving the impression that chemosynthetic microbes, or at least methane-tolerant microbes, did not participate in the carbonate production of their cap carbonate host. This apparent paradox has been an outstanding question in the lowermost Ediacaran cap carbonates of the Taoudeni Basin, NW Africa. In the Kaarta Mountains of Mali these carbonates exhibit, over short distances (<10 km), sharp facies-related environmental modifications with quiescent-dominated seafloor conditions, episodically interrupted by metre-scale disrupted substrates. The latter comprises fissure and fracture networks, occluded with tabular- and rosette-shaped barite cements, and sealed by decimetre-scale stromatolitic build-ups exhibiting intergrowths with barite needles. The strongly 13C-depleted carbon isotope values of the microbial carbonates (δ13C as low as −43.2 ‰ PDB) suggest the influence of methane, also preserved as fluid inclusions in barite crystals (documented with RAMAN spectroscopy) derived from a gas reservoir below the cap carbonate. Th of other fluid inclusions (Linkam microthermometry), ranging from 174 °C to 222 °C, provides minimum entrapment temperatures for barite precipitation. The microbially induced oxidation of methane and input of Ba-rich fluids were coupled to reduction of sulphate derived from seawater. The Sr/S isotope ratio and barite shape and size point to diagenetic barite crystals. The biomarkers yielded by the cap carbonate reflect a C29-dominant steroidal signature characteristic of stigmastanoid algal blooms. Although present-day microbial build-ups related to methane sources commonly occur in deep substrates and under anoxic bottom waters, the cap carbonate of the Kaarta Mountains is representative of shallower substrates, whereas its biomarkers point to deposition under episodic non-oxidising conditions.

Marble trace element and C-O isotope geochemistry of the Paleoproterozoic Jingshan Group, North China: Insights into BIF formation during the Lomagundi-Jatuli Event

The North China Craton, one of the oldest continental blocks in the world, comprises Paleoproterozoic metamorphic sedimentary formations that record the effects of multiple major events in early Earth history, including the Great Oxidation Event (GOE) and its consequent Lomagundi-Jatuli carbon isotope event (LJE). The lack of focused research on the geological record of LJE-equivalent rocks of the Jiaodong Peninsula, Shandong Province, eastern China, has hindered our understanding of the Precambrian atmospheric oxygen evolution recorded by rocks of the North China Craton. This paper considers carbon and oxygen isotope and trace element geochemical data recovered from marble deposits of the Paleoproterozoic Jingshan Group (2.20–1.90 Ga) of the Jiaolai Basin. The investigated strata display a pronounced positive δ13CV-PDB excursion greater than 4.2 ‰. δ13CV-PDB and δ18OV-SMOW values range from −3.7 ‰ to 5.4 ‰ and 4.5 ‰ to 18.7 ‰, respectively. Positive co-variance of carbon and oxygen isotope values of the analyzed Jingshan Group samples is interpreted to reflect the effects of metamorphism and water–rock reactions. Marble deposits of the Jingshan Group experienced recrystallization, metamorphism, and silicification resulting in strong decarbonation. High amphibolite facies metamorphism may have reduced δ13CV-PDB by 3 ‰ to 5 ‰. Thus, estimated original sedimentary δ13CV-PDB values of as great as +8.4 ‰ suggest the existence of a strong positive anomaly that may reflect the global Lomagundi-Jatuli event. Rare earth and other trace element geochemical results of the present study suggest that banded iron formation (BIF) deposits associated with the Jingshan Group marble formed in a redox stratified ocean in the Jiaolai Basin dominated by ferruginous conditions. Moreover, our results suggest that positive carbon isotope anomaly associated with the LJE is largely constrained to sediment deposited in shallow and coastal marine environments.

A climate perturbation at the Middle –Late Jurassic Transition? Evaluating the isotopic evidence from south-central England

The Jurassic greenhouse is punctuated by short cooling intervals. Some published oxygen isotope records of belemnite rostra and fish teeth have been interpreted to reveal a prominent decrease in seawater temperature during the Late Callovian–Early Oxfordian. This is in part the basis for a proposed an ice age at the Middle-Late Jurassic Transition. In contrast relatively constant oxygen isotope records and therefore seawater temperatures as well as carbon isotope values characterized by significant scatter but showing more positive values during the middle and late Callovian have been reported from elsewhere. This research has constructed a stable isotope stratigraphy (from belemnites, Gryphaea and oysters) principally from the Callovian-Oxfordian interval (from southern England) and integrated these data with existing data to assess the pattern of carbon and oxygen isotopic change. Our marine macrofossil record reveals isotopic patterns that are generally comparable with other European basins. Carbon isotopic trends are consistent with bulk carbonate carbon isotope records displaying systematic fluctuations, the largest of which (Middle Callovian, Calloviense/Jason Zones to Early Oxfordian, Mariae Zone) corresponds to previously identified phases of environmental perturbation. Such a trend may have resulted from enhanced burial and preservation of organic matter, leaving the seawater enriched in the heavy carbon isotope. Inferred cooling, derived from our oxygen isotope data from southern England, occurs within the Late Callovian and the Early Oxfordian (Athleta to Mariae zones). Cooling post-dates this positive carbon isotope excursion. Enhanced carbon burial and atmospheric carbon dioxide draw down may have induced cooling. In this study the analysis of a single region (southern England) allows critical factors controlling the oxygen isotopic composition of the carbonates (e.g. temperature and the oxygen isotopic composition of the solution from which the carbonates precipitated) to be more comparable. If Jurassic polar climates were truly warm such a degree of cooling would undoubtedly lead to cooler polar temperatures – but only with seasonal ice.

Geochemical parameters of thermal simulation of gas generation on lacustrine Type II shales in semi-open pyrolysis system

A semi-open thermal simulation of hydrocarbon generation experiment was conducted on the lacustrine Type II rocks (the Chang 7 member shale in the Ordos Basin, China). Geochemical characteristics of the hydrocarbon and non-hydrocarbon gas were studied. The yield of hydrocarbon and non-hydrocarbon gas is approximately the same in the whole process of hydrocarbon generation. The cumulative and net increased yield of the hydrocarbon gas were measured and quantified. Gas generation stages are divided and the source of the generation of different gases are studied. Carbon isotopic values of gases generated were tested. The pyrolysis residues at each temperature point were collected and subjected to routine pyrolysis analysis. Based on the experiment, the gas generation can be divided into 3 stages, and different stages have different gas source.

A laboratory observation for gases transport in shale nanochannels: Helium, nitrogen, methane, and helium-methane mixture

Mudstones are widely distributed in sedimentary basins with abundant nanopores and has very low fluid mobility. It is widely accepted that gas migration in micro-nanochannels no longer follows Darcy's law and the Hagen-Poiseuille equation and that molecular kinetic features profoundly influence gas migration in micro-nanochannels. Here, we characterize the nanochannel sizes of Longmaxi Shale cores under different overburden pressure and pore pressure conditions. And the apparent permeabilities of individual component gases (helium, nitrogen, and methane) in different size nanochannels are compared. Then the variations for components and methane carbon isotope values of the overflowing helium-methane mixture are analyzed. The results show that the molecular slippage effect contributes significantly to the transport of the three gases, especially at low pore pressures; helium has the largest apparent permeability because of its largest molecular mean free path (or Knudsen number). Methane has the smallest molecular mean free path, and the adsorption effect reduces channel size and increases surface roughness, which inhibits the molecular slip effect and therefore results in methane having the smallest apparent permeability. Helium has a transport advantage in the helium-methane mixture due to its Knudsen number advantage, and the larger Knudsen number of 12CH4 likewise leads to a transport advantage over 13CH4. This study suggests that the molecular slippage effect may be an important molecular dynamics mechanism for the efficient development of shale gas. Pressure gradient-driven transport of helium-bearing gas in nanochannels is an essential mechanism for helium enrichment, and high-grade helium reservoirs should occur in secondary low-pressure reservoirs in the basin.

Carbon isotope composition characteristics of light hydrocarbon gas from typical kerogen cracking and its application for gas source identification: A case study of the Sichuan Basin

The natural gas resources in the Sichuan Basin are abundant and exhibit various phenomena, for example, mixed sources, mixed maturities and overlapping combinations, resulting in great difficulties in identifying natural gas sources. In this study, several groups of thermal simulation experiments were conducted on various types of kerogens using closed and/or semi‐open systems to investigate the characteristics of the carbon isotope compositions of light hydrocarbon gases derived from different typical kerogens. The results showed that the carbon isotope compositions and variation trends of methane and ethane are controlled by the kerogen type, thermal simulation system and thermal evolution degree. The carbon isotope compositions of light hydrocarbon gases derived from different types of kerogens exhibit some differences with increased thermal evolution degree. When the thermal simulation temperature increases from 320 to 550°C, the methane carbon isotope of typically marine source rocks, mainly type I and type II1 kerogens, is slightly higher than or equivalent to that of ethane. However, the ethane carbon isotope of terrestrial source rocks, primarily types II2 and III kerogens, is significantly heavier than methane. By comparison, the evolution trend of carbon isotope compositions of actual natural gas is well consistent with that of light hydrocarbon gases cracked from thermal simulation experiments with increased thermal evolution degree. These findings are of great importance to identify the source rock of actual natural gas with high thermal maturities, as well as to determine the sources of deep shale gas in the southern Sichuan Basin, the Yuanba gas field and the Puguang gas field. Finally, a fitting method of carbon isotope values of methane and ethane of light hydrocarbon gases can be used to more finely differentiate the sources of natural gas in complex areas with mixed sources, mixed maturities and overlapping combinations.

The Mechanisms Controlling the CO2 Outgassing of a Karst Spring–River–Lake Continuum: Evidence from Baotuquan Spring Drainage Area, Jinan City, Northern China

The significance of CO2 emissions at the water–air interface from inland water bodies in the global carbon cycle has been recognized and is being studied more and more. Although it is important to accurately assess CO2 emission flux in a catchment, little research has been carried out to investigate the spatio-temporal variations in CO2 emissions in view of a water continuum. Here, we systematically compared the differences and control factors of CO2 degassing across the water–air interface of a spring–river–lake continuum in the discharge area of Baotuquan Spring in July 2017, which is a typical temperate karst spring area in Jinan city, northern China, using hydrogeochemical parameters, stable carbon isotope values, and CO2 degassing flux. Affected by the pCO2 concentration gradient between the water and ambient air, the spring water showed a high CO2 degassing flux (166.19 ± 91.91 mmol/(m2 d)). After the spring outlet, the CO2 degassing flux in the spring-fed river showed a slight increase (181.05 ± 155.61 mmol/(m2 d)) due to river flow rate disturbance. The river flow rate was significantly reduced by the “blockage” of the lake, which promoted the survival and reproduction of phytoplankton and provided favorable conditions for aquatic plant photosynthesis, increasing the plankton biomass in the lake to 3383.79 × 104/L. In addition, the significant decrease in the dissolved inorganic carbon (DIC) concentration and the increase in the δ13CDIC values in the lake also indicated that the photosynthesis of the lake’s aquatic plants resulted in a significant decrease in the pCO2 concentration, thus limiting the amount of CO2 off-gassing (90.56 ± 55.03 mmol/(m2 d)).

Reassessing the origin of lentil cultivation in the Pre-Pottery Neolithic of Southwest Asia: new evidence from carbon isotope analysis at Gusir Höyük

Lentils represent the most common pulse crop found in Southwest Asian Neolithic archaeobotanical assemblages. Using carbon isotope determinations and palaeoclimatic modelling this paper investigates variability and change through time in lentil growth habitats at Gusir Höyük, a Pre-Pottery Neolithic habitation site in the Upper Tigris basin of southeast Anatolia dated to the 12th and 11th millennia cal bp. The elevated lentil carbon isotope values from samples dated to ~ 10,500–10,300 cal bp possibly points to greater water availability and the potential onset of lentil cultivation at Gusir Höyük during the Early Pre-Pottery Neolithic B. The paper revisits previous hypotheses about the process and timing of initial lentil domestication in the region through a re-evaluation of materials available from other Neolithic sites in SW Asia. Its findings highlight the important role of wild lentil populations growing in higher-rainfall localities, which may have responded more readily to increasing water availability in the context of early cultivation. It also explores the potential offered by isotopic approaches for detecting early cultivation, highlighting the need for future studies on pulse and cereal crop progenitors in SW Asia and beyond.

The prospects of poop: a review of past achievements and future possibilities in faecal isotope analysis.

What can the stable isotope values of human and animal faeces tell us? This often under-appreciated waste product is gaining recognition across a variety of disciplines. Faecal isotopes provide a means of monitoring diet, resource partitioning, landscape use, tracking nutrient inputs and cycling, and reconstructing past climate and environment. Here, we review what faeces are composed of, their temporal resolution, and how these factors may be impacted by digestive physiology and efficiency. As faeces are often used to explore diet, we clarify how isotopic offsets between diet and faeces can be calculated, as well as some differences among commonly used calculations that can lead to confusion. Generally, faecal carbon isotope (δ13 C) values are lower than those of the diet, while faecal nitrogen isotope values (δ15 N) values are higher than in the diet. However, there is considerable variability both within and among species. We explore the role of study design and how limitations stemming from a variety of factors can affect both the reliability and interpretability of faecal isotope data sets. Finally, we summarise the various ways in which faecal isotopes have been applied to date and provide some suggestions for future research. Despite remaining challenges, faecal isotope data are poised to continue to contribute meaningfully to a variety of fields.

An integrative palaeoenvironmental and chronostratigraphic study of the Lower Miocene in the North Alpine Foreland Basin – Are global climate signals detectable?

Uncertainties in relation to chronostratigraphic correlations have limited our understanding of the possible impact of global-scale climate signals on the epicontinental sediments of the North Alpine Foreland Basin (NAFB). In an effort to resolve the problem, we have carried out a detailed palaeoenvironmental and chronostratigraphic study of an 18-m thick section of the marine, middle Burdigalian Neuhofen Formation (NH Fm) at Mitterdorf (SE Germany). Based on section logging, sampling of microfossils and nannoplankton, and analyses of stable oxygen and carbon isotopes, we demonstrate that significant environmental changes took place during the deposition of the NH Fm at Mitterdorf. In particular, the presence of nannoplankton zones NN3 and NN4 necessitated a re-interpretation of existing magnetostratigraphic data from Mitterdorf. To determine whether the observed environmental changes can be placed in a supra-regional and global context, a new chronostratigraphic framework was established for the study area using a multi-proxy approach based on 3-D modeling, litho-, bio-, and magnetostratigraphy, already available data, and statistical analyses of new and previously published microfossil data. The results reveal that the Mitterdorf section can be correlated with polarity chrons C5Dr.2r and C5Dr.1n and that its age is 17.78–17.65 (vs. 17.65–17.50 Ma or 17.95–17.85 Ma in earlier works). Furthermore, the results show that the deposition of the entire NH Fm took place during the interval from 18.1 to 17.6 Ma, and that the accompanying environmental changes did not occur isochronously across its range. Nevertheless, comparison of literature-based global datasets with our new data indicates that the 3rd order sea level highstand at 17.85 Ma had an impact on the environment of the NH Fm. Furthermore, transition from eutrophic, open marine to mesotrophic, shallow marine conditions at Mitterdorf coincides with minima in orbital eccentricity and global carbon isotope values at 17.67 Ma. Our results are summarized in palaeoenvironmental models of three time-points within the middle Burdigalian in the NAFB.

Charring effects on stable carbon and nitrogen isotope values on C4 plants: Inferences for archaeological investigations

Experimental studies demonstrated that charring affects stable isotope values of plant remains. Therefore, it is necessary to consider the impact of charring to reliably interpret δ13C and δ15N values in archaeobotanical remains before using this approach to reconstruct past water management, paleoclimatic changes, and infer paleodietary patterns. Research so far has focused mostly on C3 plants while the charring effect on C4 plants is less understood. This study explored the effects of charring on δ13C, δ15N, %C, %N, and C:N in grains of two C4 species, Sorghum bicolor (L.) Moench (NADP-ME) and Cenchrus americanus (L.) Morrone (heterotypic synonym Pennisetum glaucum (L.) R.Br.) (NAD-ME), grown under the same controlled environmental conditions (watering, light, atmospheric humidity). Sorghum and pearl millet grains were charred from 1 to 3 h at 200–300 °C. Comparing first the uncharred grains, the results show that sorghum has lower δ15N and higher δ13C values than pearl millet. This evidence is also recorded in the charred grains. The charring experiments indicate that the temperature to which the grains are exposed has a higher impact than time on the preservation, mass loss, %C, %N, C:N, and δ13C and δ15N values. Every 50 °C of increase resulted in significant increases of δ15N (+0.37‰) and of δ13C (+0.06‰) values. Increasing the duration of charring to 3 h resulted in significant changes of δ15N (+0.17‰) and no significant changes for δ13C (−0.04‰) values. The average charring effects estimated in our experiment is 0.27‰ (95% CI between −0.02 and 0.56) for δ15N and −0.18‰ (95% CI between −0.30 and −0.06‰) for δ13C. Considering the average values, our data show that pearl millet is more affected by charring than sorghum; however, according to the standard deviations, sorghum shows a greater variability charring effect than pearl millet. This study provides new information to correctly assessing the isotopic values obtained from ancient C4 crops, providing a charring offset specific for C4 plants. Furthermore, it suggests that NAD-ME and NADP-ME species present isotopic differences under the same growing conditions and this must be taken into account in analytical works on ancient C4 crops.

Geochemical characteristics and exploration significance of ultra-deep Sinian oil and gas from Well Tashen 5, Tarim Basin, NW China

The Well Tashen 5 (TS5), drilled and completed at a vertical depth of 9017 m in the Tabei Uplift of the Tarim Basin, NW China, is the deepest well in Asia. It has been producing both oil and gas from the Sinian at a depth of 8780–8840 m, also the deepest in Asia in terms of oil discovery. In this paper, the geochemical characteristics of Sinian oil and gas from the well were investigated and compared with those of Cambrian oil and gas discovered in the same basin. The oil samples, with Pr/Ph ratio of 0.78 and a whole oil carbon isotopic value of −31.6‰, have geochemical characteristics similar to those of Ordovician oils from the No. 1 fault in the North Shuntuoguole area (also named Shunbei area) and the Middle Cambrian oil from wells Zhongshen 1 (ZS1) and Zhongshen 5 (ZS5) of Tazhong Uplift. The maturity of light hydrocarbons, diamondoids and aromatic fractions all suggest an approximate maturity of 1.5%–1.7% Ro for the samples. The (4-+3-) methyldiamantane concentration of the samples is 113.5 μg/g, indicating intense cracking with a cracking degree of about 80%, which is consistent with the high bottom hole temperature (179 °C). The Sinian gas samples are dry with a dryness coefficient of 0.97. The gas is a mixture of kerogen-cracking gas and oil-cracking gas and has Ro values ranging between 1.5% and 1.7%, and methane carbon isotopic values of −41.6‰. Based on the equivalent vitrinite reflectance (Reqv = 1.51%–1.61%) and the thermal evolution of source rocks from the Cambrian Yu'ertusi Formation of the same well, it is proposed that the Sinian oil and gas be mainly sourced from the Cambrian Yu'ertusi Formation during the Himalayan period but probably also be joined by hydrocarbon of higher maturity that migrated from other source rocks in deeper formations. The discovery of Sinian oil and gas from Well TS5 suggests that the ancient ultra-deep strata in the northern Tarim Basin have the potential for finding volatile oil or condensate reservoirs.

The origin of cap carbonate after the Ediacaran glaciations

Cap carbonate is the most unique component of a Snowball Earth glaciation, i.e., two Cryogenian global glaciations. In the canonical model, cap carbonate precipitation requires a deglacial extremely high atmospheric pCO2 level, which is unique for a Snowball Earth glaciation but did not occur in other non-Snowball Earth glaciations. However, some Ediacaran glacial successions also have a carbonate unit directly overlying the glacial deposits, although the Ediacaran glaciation is widely accepted to be a non-Snowball Earth ice age. Therefore, occurrence of Ediacaran glacial cap carbonate is counterintuitive, challenging the traditional model of cap carbonate precipitation. Here, we investigate two Ediacaran glacial cap carbonates, i.e. the Zhoujieshan cap carbonate above the Hongtiegou glacial deposits in the Chaidam Block, and the Hankalchough cap carbonate overlying the Hankalchough glacial deposits in the Tarim Block. The Zhoujieshan cap carbonate shows a transitional contact with the underlying glacial deposits, and has a nearly invariant carbonate carbon isotope value (δ13Ccarb) of ∼ + 1‰. The Hankalchough cap carbonate from the Luobupo section has a persistent δ13Ccarb value of ∼ − 5‰, but display a ∼ 15‰ spatial isotopic gradient in the Quruqtagh area. Combining with other occurrences, the Ediacaran glacial cap carbonate differs from the Snowball Earth cap carbonate in paleogeographic distributions, sedimentary structures, and mineralogical and geochemical compositions. We noticed that the Ediacaran glacial cap carbonates were restricted at ∼30–50° N/S, which may reflect a rapid transition from glaciation to carbonate deposition in subtropics. Thus, we speculate that the Ediacaran glaciation might have extended to latitude low enough, while the subsequent deglaciation and global warming may associate with an expansion of carbonate precipitation toward higher latitudes. Thus, the Ediacaran glacial cap carbonate precipitation occurred when carbonate precipitation and glaciation spatially overlapped in subtropics. Alternatively, considering paleomagnetic evidence for a ∼ 90° reorientation of all continents due to the Ediacaran true polar wander (TPW) event, some Ediacaran glacial cap carbonates could also be driven by glaciated continents moving into lower latitudes, where glacier melt and carbonate precipitated. Either way, a typical Snowball Earth glaciation may lead to global cap carbonate depositions, while most of Phanerozoic glaciations are characterized by glacial deposits in mid- to high-latitude and carbonate precipitation in tropics, i.e., showing no spatial overlapping of glaciation and carbonate precipitation. Thus, the enigmatic cap carbonate precipitation after the Ediacaran glaciations imply a unique climatic condition that differs from either a Snowball Earth glaciation or a Phanerozoic ice age.

Early diagenetic mobilization of rare earth elements and implications for the Ce anomaly as a redox proxy

The Rare Earth Elements (REE) archived in carbonate rocks retain a wealth of information on paleo-seawater chemistry and local-regional redox conditions. However, interpretations are often ambiguous due to the potential for REE remobilization in marine environments. In this regard, many carbonate rocks that retain primary seawater isotopic signatures exhibit non-seawater-like REE patterns, implying either unusual REE behaviour in seawater or diagenetic overprinting of otherwise well-preserved rock samples. Here, we apply sequential leaching to constrain the possible effects of different REE-bearing phases on measured carbonate REE patterns in order to address this quandary. Our results show that the exchangeable phase contains negligible REE, but could be an important host phase for other elements such as Sr, Ba and K. The acidified hydroxylamine hydrochloride leach is shown here not only to dissolve Fe–Mn oxides but also phosphate minerals, which induces middle REE enrichment in corresponding leachates of dolostone samples in our study. The demonstrable Fe–Mn oxide phase in limestone samples is characterized by middle and/or light REE enrichment and positive Eu anomalies, which are attributed to hydrothermal processes and continuing exchange with marine fluids after initial precipitation. The non-seawater-like REE patterns observed in the carbonate phase of otherwise well-preserved limestones resemble those of the co-existing Fe–Mn oxide fraction, and are interpreted to reflect the dissolution of REE carrier phases during early diagenesis. This view is supported by fluid-rock interaction modelling, which shows how REE can be mobilized at relatively low fluid/rock ratios in shallow porewaters. Non-seawater-like REE patterns may therefore be caused by the incorporation of REE from shallow porewaters before final lithification due to an elevated flux of particulate REE carrier phases, e.g. Fe–Mn oxides and organic matter, to the seafloor. In spite of the sensitivity of carbonate REE patterns to early diagenetic exchange, the co-occurrence of non-seawater-like patterns with primary strontium and carbon isotope values suggests that REE should not be viewed as a general indicator for the preservation of other geochemical proxies. Importantly, Ce anomalies of the carbonate phase will also be affected by porewaters, masking primary seawater values. Our results favour a reevaluation of redox interpretations by taking into account REE patterns as a whole.

Evaluating and comparing geochemical sampling protocols in dinosaur eggshells: refining Cretaceous ecosystem research

The geochemical signatures of dinosaur eggshells represent well-established proxies in paleoenvironmental and paleobiological research. The variable sampling procedures reported in the literature, however, deserve attention. In order to evaluate the impact of different sampling methodologies on carbon and oxygen isotope and elemental concentrations, grinding was contrasted with drilling to extract powder samples from eggshell fragments collected at several locations. Eggshell data were further contrasted with surface materials, encasing matrix and compared with independent proxies using petrographic and elemental techniques. Iron and manganese elemental concentrations revealed an enrichment sequence depending on the sampling strategy for the same eggshell fragment. This pattern can be mistaken for a variable state of preservation. In contrast, carbon and oxygen isotope values exhibited only subtle differences and lacked clear trends. This suggests that isotope data are less susceptible to different methodological approaches. It is shown that drilling offers a wider range of possibilities compared to grinding (e.g., faster and less destructive). Additionally, drilled powder samples can confidently be used for elemental and isotope analysis, excluding contamination, thus providing a more accurate set of proxy data from eggshell archives.

Isotopic reconstruction of the early life experience of individuals from the early Bronze age Vliněves site (Czech Republic)

This paper provides information on the early life experience of people from the Central European Early Bronze Age, reconstructed on the basis of the stable carbon (δ13C) and nitrogen (δ15N) isotopic values from dentine serial sections of individuals from Vliněves (Czech Republic). This site yielded the largest known quantity of human remains from the Únětice culture, coming from both regular graves and settlement features. In this pilot study 27 individuals aged between 7 and 30–40 years were investigated.The average value of maximal nitrogen isotopic offset within the isotopic profile (Δ15Nmax) was 4.1 ± 1.2 ‰, which is higher than the recommended range for weaning under healthy circumstances. The reported ages at the first decrease in δ15N values, as well as at the final smoothing of the nitrogen isotopic curve, suggest that all individuals were weaned before 2.2 years of age. Most individuals (n = 20) showed positive covariance between δ15N and δ13C values during infancy and early childhood, which is the typical isotopic pattern of breastfeeding. Post-weaning isotopic values were typical for a terrestrial C3 based diet and suggest limited access to animal protein on the part of individuals buried in settlement pits. The mild increase in δ15N values in later childhood suggests that the explanation of the increased Δ15Nmax lies rather in the special character of the early childhood diet than in the common presence of nutritional/physiological stress. The similarities in the isotopic profiles of individuals from multiple burials suggest the shared dietary behaviour of these individuals.

Molecular and isotopic signatures of indigenous and non-indigenous hydrocarbons in Campanian sediments from the Tano Basin, Ghana

The Campanian source strata of the Tano Basin, Ghana, have garnered exploration interest based on the recent discoveries of hydrocarbon shows in some offshore wells. This study reports on the bulk geochemical composition (Total organic carbon content and Rock-Eval pyrolysis parameters), molecular markers, and stable carbon isotope (δ13C) composition of eleven Campanian sediments from TP–1 and Ankobra–1 well, a shallow and deep-water well in the Tano Basin respectively. Based on the analysis of total organic carbon content and Rock-Eval pyrolysis parameters (S1, S2, and Tmax), it was found that the TP-1 Campanian sediments contain indigenous hydrocarbons. Contrariwise, the Campanian samples from the Ankobra-1 well are mainly composed of non-indigenous hydrocarbons, possibly originating from offshore drilling fluid contaminants. Distribution of saturated and aromatic hydrocarbons, including normal alkanes, acyclic isoprenoids, steranes, naphthalenes, phenanthrenes, dibenzothiophene, dibenzofuran, fluorenes, and their alkyl derivatives, as well as stable carbon isotope (δ13C) values, were analyzed to gain insight into the biological source input, depositional environment, and thermal maturity of the organic matter (OM) in the sediments. The molecular and isotope results indicated that the OM in the indigenous hydrocarbons is from mixed organic sources, with a predominance of terrestrial plants, whereas lower marine organisms dominate the non-indigenous hydrocarbons. Moreover, the molecular ratios obtained from our analysis indicated that the OM present in the indigenous hydrocarbons was deposited under suboxic conditions in a marginal marine environment. Contrarily, the non-indigenous hydrocarbons exhibit a strong association with marine carbonate facies. Additionally, the maturity assessment based on biomarker ratios, indicated that the OM within the Campanian sediments from TP-1 well is in the early phase of oil generation whereas the OM in the non-indigenous hydrocarbons is in the peak-late mature phase. In conclusion, our geochemical findings have revealed the hydrocarbon potential and heterogeneity of hydrocarbons within the Tano Basin's Campanian source strata induced by non-indigenous hydrocarbons. The geochemical data obtained from our study provide evidence of the potential influence of non-indigenous hydrocarbons on the misrepresentation of source input, depositional environment, and thermal maturity of organic matter (OM) in source rock analysis.

Dietary Niche of Three Omnivorous Turtle Species in a Northern Florida River: Insights from Stable Isotope Analysis

Macrochelys suwanniensis (Suwannee Alligator Snapping Turtle) coexists with 2 other native large omnivorous turtle species (Chelydra serpentina [Snapping Turtle] and Trachemys scripta scripta [Yellow-bellied Slider]) in a 9-km section of the Santa Fe River in northern Florida. A major shift in dominant submersed aquatic vegetation prompted us to quantify trophic position and niche overlap among these 3 species. Here, we examine carbon and nitrogen isotopic values of these turtles and their potential food resources within the changing riverine system. We provide evidence of low isotopic niche overlap between M. suwanniensis and C. serpentina, whereas T. s. scripta occupied a discrete niche having lower carbon and nitrogen values.

Position-specific carbon isotopes of Murchison amino acids elucidate extraterrestrial abiotic organic synthesis networks

The Murchison meteorite is a well-studied carbonaceous chondrite with relatively high concentrations of amino acids thought to be endogenous to the meteorite, in part because they are characterized by carbon isotope (δ13C) values higher than those typical of terrestrial amino acids. Past studies have proposed that extraterrestrial amino acids in the Murchison meteorite could have formed by Strecker synthesis (for α-amino acids), Michael addition (for β-amino acids), or reductive amination, but a lack of constraints have prevented confident discrimination among these possibilities, or assignment of specific formation pathways to each of several specific amino acids. Position-specific carbon isotope analysis differentiates amongst these mechanisms by relating molecular sites to isotopically distinct carbon sources and by constraining isotope effects associated with elementary chemical reactions. Prior measurements of the position-specific carbon isotopic composition of α-alanine from the Murchison CM chondrite demonstrated that alanine’s high δ13CVPDB value is attributable to the amine carbon (δ13CVPDB = +142 ± 20‰), consistent with Strecker synthesis drawing on 13C-rich carbonyl groups in precursors (Chimiak et al., 2021). Here, we measured the δ13C composition of fragment ions generated by electron impact ionization of derivatized ⍺-alanine, β-alanine, and aspartic acid from Murchison via gas chromatography-Fourier transform mass spectrometry. α-Alanine’s amine carbon yielded δ13CVPDB = +109 ± 21‰, which is consistent with the previously measured value and with formation from 13C-rich precursors. β-Alanine’s amine carbon presents a lower δ13CVPDB = +33 ± 24‰, which supports formation from 13C-rich precursors but potentially via a Michael addition mechanism rather than Strecker synthesis. Aspartic acid’s amine carbon has δ13CVPDB = −14 ± 5‰, suggesting synthesis from precursors distinct from those that generated the alanine isomers. These measurements indicate that Murchison amino acids are a mixture of compounds made from different synthesis mechanisms, though some subsets likely drew on the same substrates; this conclusion highlights the complexity of extraterrestrial organic synthesis networks and the potential of emerging methods of isotope ratio analysis to elucidate the details of those networks.

Holocene relationships between climate, waterfowl, and lacustrine nutrient cycling at Kettle Lake, North Dakota, USA

Avian populations can substantially influence lacustrine nutrient loading and biogeochemical cycling through guano deposition. Here, we examine the influence of climate-forced avian migration throughout the Holocene on Kettle Lake, North Dakota, using stable nitrogen and carbon isotope values (δ15N, δ13C) of lake sediment organic matter. Carbon content and δ13C values are negatively correlated with δ15N and appear to be driven by changes in charcoal abundance and watershed vegetation, respectively. We find enriched δ15N values when the guano mineral struvite is present in the lake sediment core in the early to Mid-Holocene. A strong δ15N-percent Nitrogen content relationship during periods with struvite, relative to periods without struvite, indicates that guano deposition from mass bird visitations altered past nitrogen cycle processes, likely through enhanced denitrification. These results attest to the ability of waterfowl to alter lacustrine N-cycling in a mid-continental North American lake, and indicate that paleo-N data in this particular lake are recording a unique history that does not necessarily represent regional paleoenvironmental conditions. However, a significant, positive relationship between δ15N and Ambrosia and Amaranthaceae pollen abundance suggests avian visitation and its impacts on the N-cycle occurred during periods of anomalously wet summers superimposed on the background conditions of early to Mid-Holocene drought.