Stable Carbon Isotope Analysis Research Articles

Determining sugar and molasses origin by non‐exchangeable hydrogen stable isotope of ethanol and carbon isotope ratio mass spectrometry

AbstractThis study explores the differentiation of sugar and molasses produced from sugar beet and cane, which are susceptible to fraudulent labeling due to differing production costs. The research aimed to authenticate these products by botanical origin using novel analytical techniques. Utilizing ethanol isotopic measurement–isotope ratio mass spectrometry (IRMS) for non‐exchangeable hydrogen stable isotopes alongside carbon stable isotopes analysis through elemental analyzer–IRMS, the study accurately identified the origin of various sugar and molasses samples, pinpointed mislabeled goods, and determined the source of products with previously unknown provenance. These methods were also effective in revealing sugar and molasses adulteration and quantifying the extent of such fraud. The combined isotope analyses demonstrated their potential as robust tools for combating misrepresentation and adulteration in the sugar industry.

Fine-scale foraging ecology and habitat use of sympatric green and hawksbill turtles in the Western Indian ocean

Using stable isotope analysis of carbon and nitrogen of turtle tissues and putative prey items, we investigated the diet of immature green turtles and hawksbill turtles foraging in the lagoon of Aldabra Atoll, a relatively undisturbed atoll in the southern Seychelles. Aldabra offers a unique environment for understanding sea turtle ecology. Green turtles mostly consumed seagrass and brown algae while hawksbill turtles mainly consumed mangroves and invertebrates. Green turtles showed a dietary shift with size (a proxy for age). There was minimal niche overlap between species and evidence of small-scale foraging site fidelity with turtle tissue reflecting site-specific prey. This highlights the ecological importance of seagrass and mangrove habitats and suggests that turtles play a role in controlling algal biomass at Aldabra. This study is the first to closely examine the foraging ecology of these sympatric turtle species in the Western Indian Ocean, a globally important region for both species.

Trophic ecology of the greater amberjack in relation to marine environmental characteristics in Taiwanese waters illustrated by stable isotope and stomach content approach

The greater amberjack (Seriola dumerili) holds significant commercially and ecologically important large pelagic marine species in Taiwanese waters. The aim of this study was investigates its stomach contents and stable isotope signatures (δ13C and δ15N) were used to explore the trophic ecology and to detect the dietary variations by length, sex, and season and their associations with marine environmental characteristics. Utilizing a generalized additive model, we elucidate how marine environmental variables influence greater amberjack feeding habitats. Our findings revealed that the mixed layer depth and sea surface temperature explained the highest influence in the greater amberjack feeding ground. To reveal the trophic ecology of the greater amberjack and their ecosystem trophic dynamics, we used an innovative approach combining stomach content analysis (SCA) and stable isotope analysis (SIA) of carbon and nitrogen (δ13C and δ15N) coupled with Bayesian mixing model analysis. By contrast, some of the results in SIA were different from the most important food items identified in SCA; in general, they prefer to consume pelagic prey species. The Bayesian mixing models indicated that the target predator species diet structure was dominated by Trichiuridae and Leiognathidae prey species, as indicated by the highest δ15N values. The relationships of the greater amberjack weight and length were not significant with δ13C values (p > 0.05) but were significant (p < 0.001) with δ15N values. The relationships between trophic positions (TPs) in terms of length, sex, and season suggested an ontogenetic shift, with varied TP values between 4.01 and 5.18, indicating that the greater amberjack is the top-level predator species in the pelagic marine ecosystem. These findings can guide ecosystem-based adaptive fishery management and conservation because the local prey species depletion and variations in marine environmental conditions may affect greater amberjack fisheries in Taiwanese waters.

Carotenoid skin ornaments as flexible indicators of male foraging behavior in a marine predator: Variation among Mexican colonies of brown booby (Sula leucogaster)

Carotenoid-dependent ornaments can reflect animals’ diet and foraging behaviors. However, this association should be spatially flexible and variable among populations to account for geographic variation in optimal foraging behaviors. We tested this hypothesis using populations of a marine predator (the brown booby, Sula leucogaster) that forage across a gradient in ocean depth in and near the Gulf of California. Specifically, we quantified green chroma for two skin traits (foot and gular color) and their relationship to foraging location and diet of males, as measured via global positioning system tracking and stable carbon isotope analysis of blood plasma. Our three focal colonies varied in which foraging attributes were linked to carotenoid-rich ornaments. For gular skin, our data showed a shift from a benthic prey-green skin association in the shallow waters in the north to a pelagic prey-green skin association in the deepest waters to the south. Mean foraging trip duration and distance of foraging site from coast also predicted skin coloration in some colonies. Finally, brown booby colonies varied in which trait (foot versus gular skin color) was associated with foraging metrics. Overall, our results indicate that male ornaments reflect quality of diet and foraging–information that may help females select mates who are adapted to local foraging conditions and therefore, are likely to provide better parental care. More broadly, our results stress that diet-dependent ornaments are closely linked to animals’ environments and that we cannot assume ornaments or ornament signal content are ubiquitous within species, even when ornaments appear similar among populations.

Clumped and in situ carbon and oxygen isotopes of calcite as tracers for oxidation of hydrocarbons in deep siliciclastic strata

The oxidation of hydrocarbons, including methane, is part of interrelated hydrogeochemical reactions affecting the carbon budget in Earth’s crust. To investigate these processes in deep siliciclastic strata, we analyzed core samples from Lower Triassic red beds in the Mahu Sag (Junggar Basin, northwest China) by coupling petrological observations with high-resolution in situ secondary ion mass spectroscopy stable carbon and oxygen isotope analyses and clumped isotopes (Δ47) of authigenic calcite. The strata contain variable oil and gas content as well as abundant high-valence Fe and/or Mn oxides. Three sequential generations of cement occur, which are characterized as (1) non-luminescent, early diagenetic calcite (MnO &amp;lt;0.3%, δ13CVPDB [Vienna Peedee belemnite] = −5.6‰ to −4.1‰); (2) bright-orange luminescent late-stage I calcite (0.75%−5.23% MnO, δ13C = −51.4‰ to −25.8‰); and (3) dull-orange late-stage II calcite (4.10%−12.93% MnO, δ13C = −91.4‰ to −30.9‰). Clumped isotopic thermometry reveals that the calcite precipitation temperature increases successively from &amp;lt;40 °C, to 81−107 °C, to finally 107−132 °C, corresponding to three precipitation time periods: before the Late Triassic, from the Early Jurassic to the Early Cretaceous, and from the Early Cretaceous to the present, respectively. δ13C values of −55.7‰ to −25.8‰ indicate that late-stage I calcite is the final product of oxidation of both methane and C2+ hydrocarbons, whereas δ13C values as low as −91‰ indicate that late-stage II calcite is mainly derived from the thermochemical oxidation of methane (δ13C = −46.8‰ to −39.3‰) induced by high-valence Mn and/or Fe oxides. For late-stage I calcite, hydrocarbon oxidation was most likely promoted by high temperatures, although microbial oxidation cannot be completely ruled out. The higher precipitation temperature of late-stage II calcite demonstrates that the oxidation of methane requires higher activation energies than oxidation of C2+ hydrocarbons. We provide reliable geochemical evidence for thermally induced sequential oxidation of hydrocarbons within deep siliciclastic strata.

When the woolly rhinoceroses roamed East Asia: a review of isotopic paleoecology of the genus Coelodonta from the Tibetan Plateau to northern Eurasia

East Asia, being the evolutionary center of Coelodonta, offers a unique opportunity to explore the spatiotemporal paleoecologies of this genus. This study utilized bulk and serial stable carbon and oxygen isotope analyses on the Coelodonta nihowanensis and other ungulates from the Longdan fauna as well as two modern goats in the Linxia Basin, aiming to explore the paleoecology of C. nihowanensis at the periphery of the Tibetan Plateau during the Early Pleistocene. The isotopic results of these mammals indicated that C3 vegetation was possibly a major component of the local environment in the Linxia Basin, which was influenced by a seasonal summer monsoon. C. nihowanensis specimens in the Longdan fauna were possibly mixed feeders, as indicated by the wide distribution of their δ13C values and the intermediate δ18O values compared to other coexisting ungulates. Moreover, the comparison of the δ13C and δ18O values of similar taxa from the Linxia and Nihewan basins has revealed spatiotemporal differences in the paleoclimate and paleoenvironments of these two regions throughout the Early Pleistocene. This provides a holistic framework for understanding the paleoecology of the C. nihowanensis. The isotopic results of the C. nihowanensis in the Linxia and Nihewan basins suggested varied foraging ecologies across different sites and time spans during the Early Pleistocene. This underscores the adaptability of the C. nihowanensis to diverse environments from west to east in northern China. By scrutinizing the evolutionary ecological history of the woolly rhinoceroses from its ancestor, Coelodonta thibetana, to its final form, Coelodonta antiquitatis, this study sheds light on the ecological adaptation of this genus from the Pliocene to Late Pleistocene, spanning its migration from the Tibetan Plateau to northern Eurasia.

Isotopic diversity and niche patterns reveal contrasting resource use among co-occurring non-native fishes within a flow-altered African river system

AbstractClassic and contemporary trophic ecology-based studies have shown that most non-native freshwater fish species (NNS) that integrate into novel environments have the potential to influence the recipient ecosystems’ structure and function. However, the interspecific trophic interactions amongst co-occurring NNS within invaded systems remain poorly studied. Here, we used carbon (δ13C) and nitrogen (δ15N) stable isotope analyses to examine general fish trophic diversity patterns (native and non-native fishes) and to explore trophic niche patterns amongst co-occurring NNS within a flow-modified river system, the Great Fish River (South Africa). The system was characterised by isotopic variation, which revealed spatial differences in trophic complexity from uninvaded headwater tributaries to invaded mainstem and downstream sections. Two of the invaded sections, the upper mainstem of the Great Fish River (UGFR) and the Koonap River, had low isotopic overlaps between NNS and the native fish assemblages. Furthermore, co-occurring NNS in these two invaded sections had variable isotopic niche sizes and low interspecific isotopic niche overlaps, suggesting the potential for trophic differentiation. By comparison, there was evidence of high resource use patterns among NNS within the lower mainstem section of the Great Fish River (LGFR), which likely reflected trophic plasticity. Overall, results of this study provided evidence of both trophic niche differentiation (UGFR and Koonap River) and niche overlap (LGFR) as probable mechanisms of co-occurrences of the non-native fishes within different invaded sections of the Great Fish River system, and underscores the difficulties associated with predicting their trophic impacts.

Trophic ecology and small‐scale differentiation of ecological groups of franciscana dolphin, Pontoporia blainvillei, in southeastern Brazil, revealed by carbon and nitrogen stable isotopes

AbstractThe franciscana, Pontoporia blainvillei, is an endemic dolphin off the east coast of South America and is considered the most endangered cetacean in the western South Atlantic. In the present study, we analyzed the muscle tissue of 24 franciscana dolphins found on the coast of Espírito Santo (ES) between 2010 and 2019 to investigate trophic ecology using carbon and nitrogen stable isotope analysis. In addition, 127 prey were analyzed to identify the preferred prey. The most important prey species in the diet of the franciscana dolphins were Trichiurus lepturus, Chirocentrodon bleekerianus, and Pellona harroweri. The franciscana dolphins were grouped into three subareas according to where they were collected throughout the distribution: 1 (North), 2 (Center), and 3 (South). In subarea 1, the preferred prey were Stellifer spp., Isopisthus parvipinnis, and P. harroweri, while in subareas 2 and 3, the prey were similar, changing the order of preference among them (Stellifer spp., T. lepturus, and C. bleekerianus). Finally, we identify two possible ecological groups of franciscana dolphins on the coast of ES, influenced by different carbon sources. Our results improve our understanding of the franciscana dolphin's trophic ecology and habitat use, providing new information and guidelines for species conservation in the region.

Evaluating the suitability of sedimentological, geochemical, and biological proxies for reconstructing floodplain palaeohydrology

Fundamental insight into the long-term ‘geoecohydrological’ dynamics of rivers and floodplains is required for their sustainable management. To study these dynamics, a multi-proxy approach is essential. While suitable proxies are available for reconstructing floodplain geomorphology and past vegetation, the suitability of the available proxies for past hydrology to reconstruct floodplain wetness has not yet been evaluated. In this study, we apply a multi-proxy analysis combining testate amoebae and several geochemical proxies for decomposition (humification, carbon and nitrogen stable isotopes), in comparison to sedimentological (stratigraphy, loss on ignition) and palaeobotanical records, to obtain independent hydrological reconstructions of alluvial floodplains in contrasting environmental settings to explore the suitability of the available proxies for past hydrology to reconstruct floodplain wetness.This study concludes that testate amoebae cannot provide a continuous and reliable hydrological reconstruction, as they are insufficiently preserved in alluvial peat deposits. In addition, mineral particles within the tests size range hamper the analysis in mineral-dominated sediment units. As organic matter decomposition is low when water tables are high and vice versa, we expected the decomposition proxies to reflect the hydrological conditions. While the amount of humic acids appears to depend mainly on the substrate rather than the decomposition of the organic matter in it, the analyses of carbon and nitrogen stable isotopes provide promising results, for both peat and non-peat deposits.

A novel approach to estimate methanogenic pathways in biogas reactors via stable carbon isotope analysis

Two microbial pathways are responsible for most of the methane produced during anaerobic digestion: acetoclastic methanogenesis (AM) and hydrogenotrophic methanogenesis (HM) coupled with syntrophic acetate oxidation (SAO). Identifying the dominant methanogenic pathway active in a system provides the information necessary to manage and optimize productivity, stability, process control, and gas quality in biogas reactors. In this study, a modified method is proposed to estimate methanogenic pathways in different biogas systems via short-term parallel incubations with methyl-labeled acetate (2-13C-acetate). Cavity ring-down spectroscopy was applied to measure the δ13C–CH4 and δ13C–CO2 isotopic signatures of produced biogas. Preliminary experiments demonstrated that longer incubation times led to significant variations in δ13C–CH4 and δ13C–CO2 and consequently interfered with the calculated fraction of CH4 produced from HM (fHM). This variability is likely caused by the dilution of 13CH4 and 13CO2 as 2-13C-acetate is consumed, along with potential changes in organic matter quality and quantity, microbial community composition, and environmental factors such as pH, volatile fatty acid content, and ammonia levels, during longer incubations. We applied this new approach to sludge from six full-scale reactors (three mesophilic and three thermophilic) and validated its potential with consistent estimates of fHM with minimal variation. Mesophilic reactors exhibited AM dominance, while HM was the dominant pathway in thermophilic reactors, aligning with reports in the literature.

Holocene hydroclimate in highland Costa Rica: new evidence from hydrogen and carbon isotopes in n‐alkanes of terrestrial leaf waxes in a 10 000‐year sediment profile

ABSTRACTWe conducted compound‐specific stable hydrogen (δD) and carbon (δ13C) isotope analysis on n‐alkanes from terrestrial leaf waxes preserved in a 10 000‐year sediment profile from Lago de las Morrenas 1 (9.4925° N, 83.4848° W, 3480 m), a glacial lake on the Chirripó massif of the Cordillera de Talamanca in Costa Rica. Our results demonstrate millennial‐scale variations in hydroclimate across the Holocene, with drier than average conditions in the highlands during the early Holocene, but with gradually increasing precipitation; mesic conditions during the middle Holocene with a gradual drying trend; and highly variable conditions during the late Holocene. This general pattern is punctuated by several centennial‐scale manifestations of global climate events, including dry conditions during the 8200, 5200 and 4200 cal a  bp events and the Terminal Classic Drought (1200–850 cal a  bp). Our δ13C analyses demonstrate that carbon isotope signals are responding to changes in hydroclimate at the site and reinforce prior interpretations of a stable páramo plant community that established following deglaciation and persisted throughout the Holocene. The shifts in hydroclimate inferred from analyses of n‐alkanes in Lago de las Morrenas 1 sediments show correspondence with charcoal records in multiple lakes, with fires most common during drier intervals.

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. &gt;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 &gt;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.