Carbon Isotope Analysis Research Articles

Multiproxy evidence for environmental stability in the Lesser Caucasus during the Late Pleistocene

The Lesser Caucasus, situated between Asia and Europe, has long been recognised as a key region for the study of human evolution in terms of the timing and routes of dispersal, as well as, ecological adaptations. In particular, scholars have argued whether stable environments persisted in the region throughout the last glaciation, serving as a refugium for temperate biota, likely attracting human settlement and use. Here, we present the results of a multidisciplinary study of Karin Tak Cave, which contains sediments that accumulated between 48,000 and 24,000 cal yr BP. We examined biostratigraphic changes at the site by looking at the composition of fauna, which we hypothesise to be naturally accumulated, in different stratigraphic phases using traditional zooarchaeological approaches combined with collagen fingerprinting (ZooMS, Zooarchaeology by Mass Spectrometry). To gain further insights into regional palaeoenvironmental conditions, we also applied stable carbon and oxygen isotope analyses to faunal tooth enamel. The obtained results suggest that the onset of the last glaciation did not cause dramatic changes in regional environments, indicating that the Lesser Caucasus was a climatically and ecologically stable region despite significant global climatic changes during this period.

Effects of HCO3− and CO2 conversion rates on carbon assimilation strategies in marine microalgae: Implication by stable carbon isotope analysis of fatty acids

Marine microalgae are an essential component of marine plankton and critical primary producers, playing a vital role in marine ecosystems. The seawater carbonate system is a dynamic equilibrium system, and changes in any component can alter the carbonate balance. In CO2-concentrating mechanisms (CCMs), carbonic anhydrase (CA) regulates CO2 concentration by catalyzing the interconversion between CO2 and HCO3−. Therefore, limiting the activity of extracellular carbonic anhydrase (exCA) alters the rate at which carbonate equilibrium is reached and further affects the carbon assimilation process in microalgae. In this study, two different microalgae, Phaeodactylum tricornutum and Nannochloropsis oceanica, were selected to investigate the effects of changes in the carbonate system on photosynthetic carbon assimilation in microalgae by inhibiting exCA activity with acetazolamide (AZ). Inhibition of exCA activity reduces specific growth rates and photosynthetic efficiency of microalgae. The total alkalinity, HCO3− concentration, and CO2 concentration of the cultures increased with the decrease of pH, but the changes of the ribulose 1,5- bisphosphate carboxylase/oxygenase (Rubisco) activities of the two microalgae were different. In addition, the two microalgae possessed different lipid and carbohydrate synthesis strategies, but both restricted triacylglycerol (TAG) synthesis. Meanwhile, the microalgal cells had to utilize more 13CO2 when HCO3− and CO2 conversion rates were limited and restricted. This led to the continuous accumulation of 13C in fatty acids and the elevation of δ13CFAs. In conclusion, our study provides a new perspective on the role of microalgae in correlating carbonate changes with photosynthetic carbon assimilation strategies under mechanistic constraints on inorganic carbon utilization.

The Sympatric Coexistence Mechanism: A Case Study of Two Penahia Species in the Beibu Gulf, South China Sea.

The study of trophic relationships among closely related species plays an important role in deepening our understanding of the resource utilization characteristics, differentiation patterns, and population dynamics of co-occurring species in the same habitat. This research uses two congeneric fish species, Pennahia pawak and Pennahia anea, as examples. Based on a stomach content analysis and a carbon-nitrogen stable isotope analysis, a comparative analysis of their feeding habits and trophic niches is conducted. Additionally, a spatial niche analysis is employed to explore the coexistence and competitive mechanisms between these two closely related fish species. The results show that specialized feeding habits mitigate intraspecific competition as the population densities increase. The carbon and nitrogen stable isotope analysis reveals variations in the feeding habits and trophic levels with body length, indicating adaptive shifts in prey selection. Despite similar food resources, niche differentiation arises due to differences in dominant prey, facilitating coexistence. Differences in spatial niche further contribute to niche separation and coexistence. In resource-limited environments, species such as Pennahia utilize trophic and spatial niche differentiation to collectively exploit resources and achieve coexistence, with implications for fishery management favoring Pennahia resource occupancy capabilities.

Method to measure tree-ring width, density, elemental composition, and stable carbon and oxygen isotopes using one sample

Tree-ring width (RW), density, elemental composition, and stable carbon and oxygen isotope (δ13C, δ18O) are widely used as proxies to assess climate change, ecology, and environmental pollution; however, a specific pretreatment has been needed for each proxy. Here, we developed a method by which each proxy can be measured in the same sample. First, the sample is polished for ring width measurement. After obtaining the ring width data, the sample is cut to form a 1-mm-thick wood plate. The sample is then mounted in a vertical sample holder, and gradually scanned by an X-ray beam. Simultaneously, the count rates of the fluorescent photons of elements (for chemical characterization) and a radiographic grayscale image (for wood density) are obtained, i.e. the density and the element content are obtained. Then, cellulose is isolated from the 1-mm wood plate by removal of lignin, and hemicellulose. After producing this cellulose plate, cellulose subsamples are separated by knife under the microscope for inter-annual and intra-annual stable carbon and oxygen isotope (δ13C, δ18O) analysis. Based on this method, RW, density, elemental composition, δ13C, and δ18O can be measured from the same sample, which reduces sample amount and treatment time, and is helpful for multi-proxy comparison and combination research.

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

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

Food web structures of irrigated rice fields estimated from carbon and nitrogen stable isotopes: Special reference to the role of filamentous green algae as a food resource of aquatic consumers

AbstractRice fields are characterized by high algal production and dense mats of filamentous green algae, and they function as habitats for various aquatic organisms. However, how algal production supports the secondary production of aquatic consumers in rice fields has not been assessed. Herein, aquatic food web structures in two adjacent rice fields in northeastern Japan were examined using carbon and nitrogen stable isotope analyses. Filamentous algae often showed higher δ13C values (mean, −23.1‰ to −21.4‰) than other organic matter sources, including particulate organic matter, benthic microalgae, and soil organic matter (−30.1‰ to −25.4‰). A δ13C‐based isotopic mixing model estimated that among 19 taxa of herbivores and omnivores, most taxa depended on filamentous algae‐derived carbon (ca. >30%). Particularly, Peltodytes intermedius larvae, a specialist feeder for filamentous algae, showed the highest reliance (mean, 66.7%–80.0%). The microcrustacean, Ostracoda sp. also utilized a diet consisting of a substantial proportion of filamentous algae‐derived carbon (57.6%). Seven out of 10 carnivorous taxa showed reliance on filamentous algae‐derived carbon by >30%. Particularly, larvae of beetles (Berosus sp., Enochrus sp., and Hydrochara affinis) showed the highest reliance (40.2%–44.3%). They could assimilate filamentous algae‐based carbon by consuming herbivores, such as P. intermedius. Because fresh filamentous green algae were eaten less by aquatic consumers, the herbivores could consume decomposed filamentous algae rather than fresh ones. Our results suggest that filamentous algae are one of the major organic matter sources supporting secondary production in rice field food webs.

Stable isotope analyses of carbon and nitrogen in hair keratin of suspected man-eating wolves from 1880s

The so-called man-eating wolves of Turku, a pack of three wolves, reportedly killed 22 children in South-Western Finland in 1880–1881. Enormous efforts were carried out to eradicate them. In January 1882 the last remaining wolf was killed. Since then, there has been considerable debate regarding the validity and extent of the man-eating behaviour. This study aims to clarify whether man-eating behaviour can be observed from the remains of these wolves. One of the wolves was mounted in 1882 and is on display at St. Olaf’s school in Turku, enabling us to collect hair keratin samples. Additionally, hair keratin was collected from two other suspected man-eaters. We analysed carbon (δ13C) and nitrogen (δ15N) stable isotope values to study the wolf’s diet during the last months of its life. Samples from seven temporally concurrent wolves were used to construct reference values. Our analyses indicated that δ15N values of suspected man-eaters were relatively low compared to the reference sample. We could not detect clear trends in isotope ratios associated with potential man-eating behavior. We believe that this lack of distinctive patterns can be explained by the relatively minor role that man-eating played in their overall diet.

Paleoenvironmental reconstruction of the Berriasian organic-rich interval of the Vaca Muerta Formation (Neuquén Basin, Argentina): Insights for the characterization of unconventional hydrocarbon shale reservoirs

The 50 m-thick Berriasian organic-rich interval (BORI) of the Vaca Muerta Formation (Neuquén Basin, Argentina) represents one of the most attractive stratigraphic intervals for unconventional hydrocarbon exploration in the unit. Nevertheless, little is known about the environmental conditions prevailing during the accumulation of the sediments. To unravel the causes that favored the preservation of the organic matter (OM) in the BORI, a detailed multiproxy sedimentological approach was conducted. The study included the analyses of microfacies, palynological content, calpionellid-calcisphere dinocysts, mineralogy, spectral gamma-ray, inorganic geochemistry, Rock-Eval pyrolysis and stable carbon isotopes of whole rock carbonate (δ13Ccarb), and associated OM (δ13Corg). The BORI presents a late Early to early Late Berriasian age and is subdivided into a lower and upper interval. The lower interval (25.6 m-thick) is primarily formed by radiolaritic wackestones and presents higher total organic carbon (TOC) content (4.2 wt% on average), mainly in the form of amorphous OM (AOM), with variable contribution of phytoclasts. The geochemical analyses (Si, Ni, Cu, Mo, U, V) indicate high productivity of the water column and overall sea bottom anoxia. Oppositely, the upper interval (24.4 m-thick) is mostly constituted by peloidal packstones/grainstones and presents a lower TOC content (1.5 wt% on average) mainly constituted by phytoclasts, with variable contribution of AOM. A decrease of the productivity and an increase of sea bottom oxygenation is recorded based on the geochemical analyses. The high OM content of the BORI responds to the combination of high productivity of the water column and sea bottom anoxia in response to the Berriasian transgression and a worldwide paleoclimatic change towards more humid conditions. The results of our study position the BORI as an attractive interval for unconventional hydrocarbon production due to its high TOC, low bulk clay mineral and high biogenic quartz content, granting an adequate geomechanical behavior.

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.

Anaerobic dihydrogen consumption of nutrient-limited aquifer sediment microbial communities examined by stable isotope analysis

ABSTRACT The biogeochemical consequences of dihydrogen (H2) underground storage in porous aquifers are poorly understood. Here, the effects of nutrient limitations on anaerobic H2 oxidation of an aquifer microbial community in sediment microcosms were determined in order to evaluate possible responses to high H2 partial pressures. Hydrogen isotope analyses of H2 yielded isotope depletion in all biotic setups indicating microbial H2 consumption. Carbon isotope analyses of carbon dioxide (CO2) showed isotope enrichment in all H2-supplemented biotic setups indicating H2-dependent consumption of CO2 by methanogens or homoacetogens. Homoacetogenesis was indicated by the detection of acetate and formate. Consumption of CO2 and H2 varied along the differently nutrient-amended setups, as did the onset of methane production. Plotting carbon against hydrogen isotope signatures of CH4 indicated that CH4 was produced hydrogenotrophically and fermentatively. The putative hydrogenotrophic Methanobacterium sp. was the dominant methanogen. Most abundant phylotypes belonged to typical ferric iron reducers, indicating that besides CO2, Fe(III) was an important electron acceptor. In summary, our study provides evidence for the adaptability of subsurface microbial communities under different nutrient-deficient conditions to elevated H2 partial pressures.

Effects of thinning and understory removal on water use efficiency of Pinus massoniana: evidence from photosynthetic capacity and stable carbon isotope analyses

Effects of thinning and understory removal on water use efficiency of Pinus massoniana: evidence from photosynthetic capacity and stable carbon isotope analyses

Impacts of anthropogenic eutrophication on the carbon transfers in lacustrine food webs: A paleolimnological assessment in four mountain lakes

Over the last decades, the intensification of anthropogenic activities and associated disturbances on lake watersheds have led to major changes in lakes trophic functioning through accelerated eutrophication. In many lakes, these changes are characterized by an unprecedented increase in organic carbon fluxes, potentially leading to a shift in biogeochemical cycles and in the balance between carbon sequestration and greenhouse gas emissions. Understanding the response of the carbon cycle to natural and anthropogenic environmental changes is becoming a crucial challenge in the context of increasing global pressures. In this study, we reconstructed the changes in the trophic functioning of the benthic and pelagic food web, in response to accelerated eutrophication in four lakes over the last millenium. Changes in carbon pathways in food webs were assessed using stable carbon isotope analysis of chitinous subfossil remains of Daphnia, Bosmina, and Chironomini archived in sedimentary records. Changes in the trophic state were inferred from sedimentary geochemical analysis, including carbon accumulation rates, Chl a accumulation rates and carbon-to-nitrogen ratios. Agro-pastoral activities were tracked by analysis of coprophilous ascospores. Results provided by this multi-proxy approach highlight recent disruptions in carbon sources and transfer pathways in lakes food webs. In particular, changes in the carbon isotopic signature of pelagic consumers suggest a recent increase in the use of 13C-depleted carbon sources such as methanogenic or respiration-derived carbon linked to recent changes in trophic state under the intensification of anthropogenic pressures.

Benthic foraminiferal assemblages in the coastal zone of the yellow river delta: Environmental significance and characteristics of microbial diversity

Unicellular eukaryotes known as benthic foraminifera have sophisticated survival mechanisms and ecological environmental indicators. Ten surface samples from the Yellow River Delta's coastal region were taken for this study to analyze the distribution of foraminifera in relation to environmental factors and to examine their microbial diversity. We looked at the physicochemical aspects of the environment at each sampling site (such as pH, TN, TOC, EC, δ13C, δ15N, PAHs, etc.), and we employed 16S rRNA high-throughput sequencing analysis to look into the interactions between microbial communities and foraminiferal species. The findings demonstrated that the Yellow River Delta's advantage benthic foraminiferal species were Quinqueloculina complanata, Ammonia beccarii, and Ammonia aomoriensis, and that TOC and TN were significant determinants of the distribution of benthic foraminiferal communities. PAH enrichment in the coastal zone effects on microbial communities and benthic foraminifera are not yet readily apparent. Sediment organic carbon and nitrogen isotope analysis revealed that marine plankton may be the dominant source of organic matter in the coastal zone sediments in the research area, which was made up of both land-based and marine organic matter. It implies that foraminifera have some environmental indicators, especially when combined with the distributional traits of the benthic foraminiferal assemblages and their considerable association with environmental parameters. The findings revealed that Q. complanata was found in the Yellow River water-affected estuarine coastal zone, A. aomoriensis was significantly influenced by sediment organic matter content and reflected the estuarine and nearshore environments and the combination of Ammonia beccarii-Ammonia aomoriensis-Elphidium excavatum assemblage indicated a semi-open intertidal shallow marine environment. Additionally, benthic foraminifera showed a responsive association with microorganisms, indicating that microbial diversity may be one of the driving forces behind benthic foraminifera's ability to adjust to environmental changes. The findings of this study will open up new avenues for research into the environmental importance of coastal zone ecosystems and for understanding how benthic foraminiferal communities survive.

Disclosing phototransformation mechanisms of decabromodiphenyl ether (BDE-209) in different media by simulated sunlight: Implication by compound-specific stable isotope analysis.

As one of the typical brominated flame retardants, decabromodiphenyl ether (BDE-209) has been widely detected in environment. However, scarce information was available on BDE-209 phototransformation mechanisms in various media. In this study, compound-specific stable isotope analysis was first applied to investigate BDE-209 phototransformation in n-hexane, MeOH:H2O (v:v, 8:2), and simulated seawater by simulated sunlight. BDE-209 transformation followed pseudo-first-order kinetic, with degradation rate in the following of n-hexane (2.66 × 10-3min-1) > simulated seawater (1.83 × 10-3min-1) > MeOH:H2O (1.41 × 10-3min-1). Pronounced carbon isotope fractionation was first observed for BDE-209 phototransformation, with carbon isotope enrichment factors (εC) of -1.01 ± 0.14‰, -1.77 ± 0.26‰, -2.94 ± 0.38‰ in n-hexane, MeOH:H2O and simulated seawater, respectively. Combination analysis of products and stable carbon isotope, debromination with cleavage of C-Br bonds as rate-limiting step was the main mechanism for BDE-209 phototransformation in n-hexane, debromination and hydroxylation with cleavage of C-Br bonds as rate-limiting steps in MeOH:H2O, and debromination, hydroxylation and chlorination in simulated seawater. This present study confirmed that stable carbon isotope analysis was a robust method to discovery the underlying phototransformation mechanisms of BDE-209 in various solutions.

Source apportionment of suspended particulate matter (PM1, PM2.5 and PM10) collected in road and tram tunnels in Krakow, Poland.

Here, we present the results of a comprehensive study of air quality in two tunnels located in the city of Krakow, southern Poland. The study comprised three PM fractions of suspended particulate matter (PM1, PM2.5 and PM10) sampled during campaigns lasting from March 14 to April 24, 2016 and from June 28 to July 18, 2016, in the road tunnel and the tram tunnel, respectively. The collected samples had undergone comprehensive chemical, elemental and carbon isotope analyses. The results of these analyses gave the basis for better characterization of urban transport as a source of air pollution in the city. The concentrations of particulate matter varied, depending on the analysed PM fraction and the place of sampling. For the tram tunnel, the average concentrations were 53.2µg·m-3 (PM1), 73.8µg·m-3 (PM2.5), 96.5µg·m-3 (PM10), to be compared with 44.2µg·m-3, 137.7µg·m-3, 221.5µg·m-3, respectively, recorded in the road tunnel. The isotope-mass balance calculations carried out separately for the road and tram tunnel and for each PM fraction, revealed that 60 to 79% of carbon present in the samples collected in the road tunnel was associated with road transport, to be compared with 15-33% obtained in the tram tunnel. The second in importance were biogenic emissions (17-21% and 41-49% in the road and tram tunnel, respectively. Sixteen different polycyclic aromatic hydrocarbons (PAHs) have been identified in the analysed samples. As expected, much higher concentrations of PAHs were detected in the road tunnel when compared to the tram tunnel. Based on the analysed PAHs concentrations, health risk assessment was determined using 3 different types of indicators: carcinogenic equivalent (CEQ), mutagenic equivalent (MEQ) and toxic equivalent (TEQ).

Organic geochemical heterogeneity of cretaceous mudrocks and reassessment of oil sources in the Tano Basin, Ghana

The Tano Basin in Ghana, situated within the South Atlantic margin, is a significant area for petroleum exploration. Previous studies have recognized the presence of source rocks rich in organic matter from the Cretaceous period in this basin. However, the specific origins of this organic matter, as well as the thermal maturity and depositional environment of the Cretaceous source strata, are not well characterized in existing literature. Here, geochemical data are reported on the bulk geochemical composition of 45 Maastrichtian to Albian-aged rock cuttings via pyrolysis and total organic carbon (TOC) analysis. Out of these samples, 29 were selected for further biomarker and stable carbon isotope (δ13C) analysis. The biomarker and isotopic signatures of the 29 rock extracts and 6 crude oils from the basin's productive Jubilee and TEN oil fields were compared to establish oil-oil and oil-source correlations. The Cenomanian and Turonian source rocks showed the greatest oil generation potential based on current bulk geochemical analysis. These rocks are dominated by oil-prone organic matter and are at a more favorable maturity stage compared to the Maastrichtian, Santonian, and Coniacian (M-S-C) rock suites. In contrast, the Albian rock samples, characterized by mixed Type II/III and Type III kerogen, and their high thermal maturity, indicate a high potential for the generation of gaseous hydrocarbons. The biomarker and isotope data from the Cenomanian, Turonian, and Albian (T-C-A) source rocks suggest that they were deposited in a Transitional Marine-Lacustrine environment characterized by reducing redox conditions. This environment effectively preserved organic matter from diverse sources such as bacteria, algae, and higher plants. Furthermore, biomarker ratios indicated that the T-C-A source rocks are in the early-peak mature window. On the other hand, the M-S-C source rocks appear to have been deposited under suboxic conditions in a Coastal Marine environment. Lower aquatic organisms dominate these rocks, which have an immature to marginally mature level. The analysis of lower molecular weight hydrocarbons (≤C20), characterized by an unresolved complex mixture, did not reveal any obvious correlation between the oils and the Cretaceous source rocks. However, the analysis of higher molecular weight hydrocarbons (≥C20) and isotopic ratios indicated that the commercial discoveries in the Jubilee and TEN fields share a genetic similarity and are primarily sourced from the T-C-A source rocks. Furthermore, the molecular and isotopic characteristics suggest that the M-S-C source rocks do not appear to have contributed to the oils found in the Jubilee and TEN fields. These new geochemical findings shed light on the paleoenvironmental conditions and source rock characteristics of the region, significantly contributing to our understanding of the petroleum evolution and potential of the Tano Basin.

Life-history of Palaeoloxodon antiquus reveals Middle Pleistocene glacial refugium in the Megalopolis basin, Greece

The Balkans are considered a major glacial refugium where flora and fauna survived glacial periods and repopulated the rest of Europe during interglacials. While it is also thought to have harboured Pleistocene human populations, evidence linking human activity, paleoenvironmental indicators and a secure temporal placement to glacial periods is scant. Here, we present the first intra-tooth multi-isotope analysis for the European straight-tusked elephant Palaeoloxodon antiquus, on an adult male individual excavated in association with lithic artefacts at the MIS 12 site Marathousa 1 (Megalopolis basin, Greece). The studied find also exhibits anthropogenic modifications, providing direct evidence of hominin presence. We employed strontium, carbon and oxygen isotope analysis on enamel bioapatite to investigate its foraging and mobility behaviour, using a sequential sampling strategy along the tooth growth axis of the third upper molar, to assess ecological changes during the last decade of life. We found a geographically restricted range, in a C3-dominated open woodland environment, and relatively stable conditions over the examined timeframe. Our results show that, despite the severity of the MIS 12 glacial, the Megalopolis basin sustained a mesic habitat, sufficient plant cover and limited seasonal fluctuations in resource availability, pointing to its role as a glacial refugium for both fauna and hominins.

Neolithisation through bone: Stable isotope analysis of human and faunal remains from Syltholm II, Lolland, Denmark

Despite an increasing number of studies, the application of stable sulfur (δ34S) isotope analysis to prehistoric bone collagen remains in its infancy. Conventionally, stable sulfur isotope compositions reflect coastal proximity and the interaction between humans and animals. Here, we undertook stable carbon (δ13C), nitrogen (δ15N) and sulfur (δ34S) isotope analysis of human and faunal bone collagen. To understand the local environmental conditions as well as the husbandry regime employed by the first farmers, and investigate where the animals were raised or hunted in non-specific terms, we sampled 50 faunal, including wild and domestic taxa, and human remains from the Late Mesolithic to Early-Middle Neolithic (c. 4860–2310 cal BC) site of Syltholm II on the island of Lolland, Denmark. We show that the wild animals were obtained from multiple locations surrounding the prehistoric Syltholm Fjord, including forested and open landscapes, areas impacted by sea spray and saltmarshes. In contrast, the domestic taxa, especially cattle, were tightly managed for the majority of their lives based on their δ13C and δ15N isotope compositions, though were likely raised in multiple locations, including sea spray-affected areas, saltmarshes and wetlands, based on their δ34S values. The domestic dogs had a broad range of δ13C, δ15N and δ34S values, reflecting the consumption of varying degrees of marine foodstuffs, including animals that were sulfide-derived. Overall, our results contribute to a growing body of evidence for possible cultural and animal husbandry duality during the earliest Neolithic in southern Scandinavia.

Carbon Isotopic Behavior During Hydrocarbon Expulsion in Semiclosed Hydrous Pyrolysis of Type I and Type II Saline Lacustrine Source Rocks in the Jianghan Basin, Central China

Abstract Organic carbon isotopic analysis is a significant approach for oil-source correlation, yet organic carbon isotopic behavior during oil expulsion from saline lacustrine source rocks is not well constrained, and this hinders its wide application for fingerprinting oils generated by saline lacustrine source rock. To resolve this puzzle, semiclosed hydrous pyrolysis was conducted on typical saline lacustrine source rocks from the Qianjiang Formation (type I kerogen) and Xingouzui Formation (type II kerogen) sampled in the Jianghan Basin, China, under high-temperature high-pressure conditions (T = 275℃–400℃; P = 65–125 MPa). Experimental results show that there is minor carbon isotopic fractionation (<3‰) between pyrolyzed and nonpyrolyzed retained oil fractions during the main oil generation/expulsion stage of both type I and II source rocks. Carbon isotopic fractionations between expelled and retained oil fractions are also minor (<2‰) during this stage. The δ13C values of retained and expelled oil fractions generated by the type I saline lacustrine source rock correlate positively with the degree of oil expulsion, whereas the influence of oil expulsion on the δ13C values of oil fractions generated by the type II source rock was not consistent. In addition, carbon isotopic analysis also unravels the mixing of oil-associated gases with different maturity levels and/or generated via different processes. Outcomes of this study demonstrate that oil expulsion from type I and II saline lacustrine source rocks cannot be able to result in large-degree carbon isotopic fractionation, indicating that carbon isotopic analysis is a feasible approach for conducting oil-source correlation works in saline lacustrine petroleum systems.

Implications of dietary carbon incorporation in fish carbonates for the global carbon cycle

Marine bony fish are important participants in Earth's carbon cycle through their contributions to the biological pump and the marine inorganic carbon cycle. However, uncertainties in the composition and magnitude of fish contributions preclude their integration into fully coupled carbon-climate models. Here, we consider recent upwards revisions to global fish biomass estimates (2.7–9.5×) and provide new stable carbon isotope measurements that show marine fish are prodigious producers of carbonate with unique composition. Assuming the median increase (4.17×) in fish biomass estimates is linearly reflected in fish carbonate (ichthyocarbonate) production rate, marine fish are estimated to produce between 1.43 and 3.99 Pg CaCO3 yr−1, but potentially as much as 9.03 Pg CaCO3 yr−1. Thus, marine fish carbonate production is equivalent to or potentially higher than contributions by coccolithophores or pelagic foraminifera. New stable carbon isotope analyses indicate that a significant proportion of ichthyocarbonate is derived from dietary carbon, rather than seawater dissolved inorganic carbon. Using a statistical mixing model to derive source contributions, we estimate ichthyocarbonate contains up to 81 % dietary carbon, with average compositions of 28–56 %, standing in contrast to contents <10 % in other biogenic carbonate minerals. Results also indicate ichthyocarbonate contains 5.5–40.4 % total organic carbon. When scaled to the median revised global production of ichthyocarbonate, an additional 0.08 to 1.61 Pg C yr−1 can potentially be added to estimates of fish contributions to the biological pump, significantly increasing marine fish contributions to total surface carbon export. Our integration of geochemical and physiological analyses identifies an overlooked link between carbonate production and the biological pump. Since ichthyocarbonate production is anticipated to increase with climate change scenarios, due to ocean warming and acidification, these results emphasize the importance of quantitative understanding of the multifaceted role of marine fish in the global carbon cycle.