Low Carbon Isotope Ratios Research Articles

The Carbon Isotopic Composition of Archean Kerogen and Its Resilience Through the Rock Cycle

The Archean rock record is limited and there is minimal organic matter available to understand the origin and evolution of life on early Earth. Low carbon isotope ratios have been measured in organic and reduced carbon phases in Archean rocks and have been invoked as biosignatures. However, it can be challenging to distinguish whether these low values reflect biotic formation, abiotic reactions, or post-depositional processes. To re-address this long-standing question, we compiled a comprehensive dataset of carbon isotope ratio measurements from organic carbon phases from Archean units that were analyzed using a variety of geochemical techniques. Our compilation also includes available descriptions and measurements of the stratigraphy, mineralogy, elemental ratios, and metamorphic grade for each data point. Our statistical analyses re-enforce a result that has been noted by prior compilations, that the carbon isotopic composition of Archean organic matter (OM) is broadly more 13C-deplete than the composition of Phanerozoic OM: The median δ13C values ( ±SD) of Archean total organic carbon and kerogen were −30.5±8‰ (n=2421) and −33.7±11.3‰ (n=556; Phanerozoic OM δ13C ±SD = −26.7±4.6‰ with n=449 from a prior compilation). Our study also identifies a previously unrecognized bimodality within the δ13C values of Archean OM that is observed even with subsampling of the data to account for geographic and stratigraphic sampling bias. We describe and model the isotopic and structural changes associated with the transformation of marine Type II kerogen from formation through diagenesis, catagenesis and metagenesis, and metamorphism, as described by trends on a van Krevelin diagram. Empirically, early maturation of organic matter during diagenesis results in shifts up to a few per-mille, which can occur in either direction depending on selective preservation and degradation of compounds. Thermal cracking that occurs during catagenesis can drive increases in δ13C of 5–12‰. At temperatures above greenschist metamorphism, carbon atoms exchange with other reactive carbon pools, driving increases in δ13C of up to 20‰. Together, our analyses suggest that the most metamorphosed graphitic samples from the earliest Archean are likely signatures of alteration, while low and multimodal ranges of δ13C values may preserve records of Archean ecology.

Roseate Terns Sterna dougallii on the southeast coast of South Africa: information on moult and migratory status

Determining the migratory status of seabird populations is crucial for addressing conservation concerns. The Roseate Tern Sterna dougallii is considered endangered in South Africa in view of its small breeding population and the threats to eggs and chicks. Earlier works based on capture-recapture data suggest that this population adopts a partial migratory strategy. Updated capture-recapture data were combined with new data on moult and stable isotopes of scapular feathers to determine whether subpopulations could be identified in the South African breeding population. Moult data on 404 individuals failed to identify subpopulations, but two groups were identifiable with the stable isotopes: one group of four individuals exhibiting low carbon and nitrogen stable isotope ratios and a second group (comprising the remaining 152 individuals) with significantly higher ratios. The isotope data suggest that birds from the two groups moulted in different areas. Comparisons with published studies showed that the 152 individuals had likely moulted their scapulars in South African waters, but the moulting area for the remaining four individuals could not be ascertained due to the absence of detailed isoscapes in the southern part of the Mozambique Channel. Further work investigating the genetic differentiation between South African and Madagascan Roseate Terns may bring new insight into the migratory behaviour of the South African population.

Super lithium-rich K giant with low 12C to 13C ratio

Context. The lithium abundances in a few percent of giants exceed the value predicted by the standard stellar evolution models, and the mechanisms of Li enhancement are still under debate. The Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) survey has obtained over six million spectra in the past five years, and thus provides a great opportunity to search these rare objects and to more clearly understand the mechanisms of Li enhancement. Aims. The aim of this work is to accurately measure the Li abundance and investigate the possible mechanisms of Li enrichment for a newly found super Li-rich giant, TYC 3251-581-1, located near the luminosity function bump with a low carbon isotopic ratio. Methods. Based on the high-resolution spectrum we obtained the stellar parameters (Teff, logg, [Fe/H]), and determined the elemental abundances of Li, C, N, α, Fe-peak, r-process, s-process elements, and the projected rotational velocity. For a better understanding of the effect of mixing processes, we also derived the 12C to 13C ratio, and constrained the evolutionary status of TYC 3251-581-1 based on the BaSTI stellar isochrones. Results. The super Li-rich giant TYC 3251-581-1 has A(Li) = 3.51, the average abundance of two lithium lines at λ = 6708 Å and 6104 Å based on the non-local thermodynamic equilibrium analysis. The atmospheric parameters show that our target locates on the luminosity function bump. The low carbon isotopic ratio (12C∕13C = 9.0), a slow rotational velocity vsini = 2.2 km s−1, and no sign of IR excess suggest that additional mixing after first dredge up (FDU) should occur to bring internal synthesized Li to the surface. The low carbon ([C∕Fe] ~−0.34) and enhanced nitrogen ([N∕Fe] ~ 0.33) are also consistent with the sign of mixing. Conclusions. Given the evolutionary stage of TYC 3251-581-1 with the relatively low 12C∕13C, the internal production which replenishes Li in the outer layer is the most likely origin of Li enhancement for this star.

The impact of the revised17O(p,α)14N reaction rate on17O stellar abundances and yields

Context. Material processed by the CNO cycle in stellar interiors is enriched in 17O. When mixing processes from the stellar surface reach these layers, as occurs when stars become red giants and undergo the first dredge up, the abundance of 17O increases. Such an occurrence explains the drop of the 16O/17O observed in RGB stars with mass larger than 1.5 M_\solar. As a consequence, the interstellar medium is continuously polluted by the wind of evolved stars enriched in 17O . Aims. Recently, the Laboratory for Underground Nuclear Astrophysics (LUNA) collaboration released an improved rate of the 17O(p,alpha)14N reaction. In this paper we discuss the impact that the revised rate has on the 16O/17O ratio at the stellar surface and on 17O stellar yields. Methods. We computed stellar models of initial mass between 1 and 20 M_\solar and compared the results obtained by adopting the revised rate of the 17O(p,alpha)14N to those obtained using previous rates. Results. The post-first dredge up 16O/17O ratios are about 20% larger than previously obtained. Negligible variations are found in the case of the second and the third dredge up. In spite of the larger 17O(p,alpha)14N rate, we confirm previous claims that an extra-mixing process on the red giant branch, commonly invoked to explain the low carbon isotopic ratio observed in bright low-mass giant stars, marginally affects the 16O/17O ratio. Possible effects on AGB extra-mixing episodes are also discussed. As a whole, a substantial reduction of 17O stellar yields is found. In particular, the net yield of stars with mass ranging between 2 and 20 M_\solar is 15 to 40% smaller than previously estimated. Conclusions. The revision of the 17O(p,alpha)14N rate has a major impact on the interpretation of the 16O/17O observed in evolved giants, in stardust grains and on the 17O stellar yields.

HD 16771: A lithium-rich giant in the red-clump stage

Aims: We report the discovery of a young lithium rich giant, HD 16771, in the core-helium burning phase that does not seem to fit existing proposals of Li synthesis near the luminosity function bump or during He-core flash. We aim to understand the nature of Li enrichment in the atmosphere of HD 16771 by exploring various Li enhancement scenarios. Methods: We have collected high-resolution echelle spectra of HD 16771 and derived stellar parameters and chemical abundances for 27 elements by either line equivalent widths or synthetic spectrum analyses. Results: HD 16771 is a Li-rich (log(n(Li))=+2.67+/-0.10 dex) intermediate mass giant star (M=2.4+/-0.1 Msun) with age=0.76+/-0.13 Gyr and located at the red giant clump. Kinematics and chemical compositions are consistent with HD 16771 being a member of the Galactic thin disk population. The non-detection of 6Li(< 3%), a low carbon isotopic ratio (12C/13C=12+/-2), and the slow rotation (vsini=2.8 km/s) all suggest that lithium might have been synthesized in this star. On the contrary, HD 16771 with a mass of 2.4 Msun has no chance of encountering luminosity function bump and He-core flash where the possibility of fast deep-mixing for Li enrichment in K giants has been suggested previously. Conclusions: Based of the evolutionary status of this star, we discuss the possibility that 7Li synthesis in HD 16771 is triggered by the engulfment of close-in planet(s) during the RGB phase.

Geometry and lithofacies of coarse-grained injectites and extrudites in a late Pliocene trench-slope basin on the southern Boso Peninsula, Japan

This study investigates the geometry and internal structures of coarse- to very coarse-grained volcanic sandstones and volcanic breccias with many siltstone clasts (interpreted to be sill-like injectites and extrudites) occurring in an upper Pliocene trench-slope basin succession on the southern Boso Peninsula, Japan. The injectites occur in the uppermost Shiramazu Formation, and pinch out laterally into siltstone-dominated deposits of the Mera Formation. Their thicknesses vary from a few centimeters to ~2m. The basal and upper contacts of the injectites with host muddy deposits are sharp and/or erosional, and are locally discordant with the bedding of the host deposits. Siltstone clasts, which were ripped up or ripped down from the host muddy deposits, are commonly incorporated into the injectites, although some siltstone clasts have geological ages older than those of the host deposits. Seven lithofacies have been identified in the injectites based on the internal structures. The combinations of internal structures are different from those of high-density turbidity current deposits and debrites, and suggest that injection was promoted by a combination of turbulent and laminar flow conditions.The extrudites show an overall convex-up geometry and possess lithological features similar to those of the injectites. They have been identified in the Rendaiji Conglomerate Member, which is encased in the Mera Formation, and which rests on the uppermost Shiramazu Formation. The extrudites are characterized by gently undulating waveforms that show upstream migration and climbing stacking patterns similar to the cross-sectional geometry of cyclic steps or upstream-migrating antidunes. The active eruption of solid–liquid mixtures onto the seafloor and sedimentary piles may have subsequently collapsed to produce supercritical high-density gravity currents down the flanks of a neptunian volcano.The injectites and extrudites locally contain Calyptogena shells and shell fragments, as well as fragments of carbonate concretions that exhibit low carbon isotopic ratios, suggesting that fluidization of the source sediments was triggered by a combination of seepage of cold methane-bearing water into the source sediments and seismic shaking. Volcaniclastic deposits older than the host muddy deposits are present in the trench-slope basin deposits and these are the likely source of the injectites and extrudites.

The stable carbon isotopic composition of Daphnia ephippia in small, temperate lakes reflects in‐lake methane availability

AbstractDaphnia can ingest methane‐oxidizing bacteria and incorporate methanogenic carbon into their biomass, leading to low stable carbon isotope ratios (expressed as δ13C values) of their tissue. Therefore, δ13C analysis of Daphnia resting eggs (ephippia) in lake sediment records can potentially be used to reconstruct past in‐lake availability of methane (CH4). However, detailed multilake studies demonstrating that δ13C values of recently deposited Daphnia ephippia (δ13Cephippia) are systematically related to in‐lake CH4 concentrations ([CH4]aq) are still missing. We measured δ13Cephippia from surface sediments of 15 small lakes in Europe, and compared these values with late‐summer [CH4]aq. δ13Cephippia ranged from −51.6‰ to −25.9‰, and was strongly correlated with [CH4]aq in the surface water and above the sediment (r −0.73 and −0.77, respectively), whereas a negative rather than the expected positive correlation was found with δ13C values of carbon dioxide (CO2) (r −0.54), and no correlation was observed with [CO2]aq. At eight sites, offsets between δ13 and δ13Cephippia exceeded offsets between δ13 and δ13Calgae reported in literature. δ13Cephippia was positively correlated with δ13C values of sedimentary organic matter (r 0.54), but up to 20.7‰ lower in all except one of the lakes (average −6.1‰). We conclude that incorporation of methanogenic carbon prior to ephippia formation must have been widespread by Daphnia in our study lakes, especially those with high [CH4]aq. Our results suggest a systematic relationship between δ13Cephippia values and [CH4]aq in small temperate lakes, and that δ13Cephippia analysis on sediment records may provide insights into past changes in in‐lake [CH4]aq.

A super lithium-rich red-clump star in the open cluster Trumpler 5

Context. The existence of lithium-rich low-mass red giant stars still represents a challenge for stellar evolution models. Stellar clusters are privileged environments for this kind of investigation. Aims. To investigate the chemical abundance pattern of the old open cluster Trumpler\,5, we observed a sample of four red-clump stars with high-resolution optical spectrographs. One of them (#3416) reveals extremely strong lithium lines in its spectrum. Methods. One-dimensional, local thermodynamic equilibrium analysis was performed on the spectra of the observed stars. A 3D-NLTE analysis was performed to derive the lithium abundance of star #3416. Results. Star #3416 is super Li-rich with A(Li)=3.75\,dex. The lack of $^6$Li enrichment ($^6$Li/$^7$Li$<$2%), the low carbon isotopic ratio ($^{12}$C/$^{13}$C=14$\pm$3), and the lack of evidence for radial velocity variation or enhanced rotational velocity ($v\sin i = 2.8\,$\kms) all suggest that lithium production has occurred in this star through the Cameron & Fowler mechanism. Conclusions. We identified a super Li-rich core helium-burning, red-clump star in an open cluster. Internal production is the most likely cause of the observed enrichment. Given the expected short duration of a star's Li-rich phase, enrichment is likely to have occurred at the red clump or in the immediately preceding phases, namely during the He-flash at the tip of the red giant branch (RGB) or while ascending the brightest portion of the RGB.

Anticorrelation between low δ13C of eclogitic diamonds and high δ18O of their coesite and garnet inclusions requires a subduction origin

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High-Resolution Spectroscopy of Cool Carbon-Rich and Metal-Poor Star HD 209621

Abstract Element abundances for HD 209621 obtained earlier display significant discrepancies, especially in the case of CNO and neutron-capture elements. Therefore we performed a detailed analysis of chemical composition of this star using a new high-resolution spectrum. Atmospheric parameters and abundance pattern are updated, and the mechanism of nucleosynthesis is examined. Abundances for 11 elements are calculated for the first time. The method of atmospheric models and spectral synthesis was used. The following values of atmospheric parameters are derived: Teff = 4400 K, log g = 1.0 (cgs) and ξt = 1.9 kms−1. The iron abundance of the star was found to be low, at [Fe/H] = -1.91±0.10. The carbon to oxygen ratio is high, C/O ≃ +2.0. Low carbon to nitrogen ratio, [C/N] ≃ -0.8, and low carbon isotopic ratio, 12C/13C = 17 ±5, are in agreement with the theory of nucleosynthesis of intermediate-mass AGB stars. The barium to europium ratio is high, [Ba/Eu] = +0.28, and is typical for carbon-enhanced metal-poor CEMP-r/s stars. The observed abundance pattern of neutron capture elements is reproduced well by the scaled solar system abundances.

High‐temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry: simultaneous measurement of the stable isotopes of oxygen and carbon in cellulose

Stable isotope analysis of cellulose is an increasingly important aspect of ecological and palaeoenvironmental research. Since these techniques are very costly, any methodological development which can provide simultaneous measurement of stable carbon and oxygen isotope ratios in cellulose deserves further exploration. A large number (3074) of tree-ring α-cellulose samples are used to compare the stable carbon isotope ratios (δ(13)C) produced by high-temperature (1400°C) pyrolysis/gas chromatography (GC)/isotope ratio mass spectrometry (IRMS) with those produced by combustion GC/IRMS. Although the two data sets are very strongly correlated, the pyrolysis results display reduced variance and are strongly biased towards the mean. The low carbon isotope ratios of tree-ring cellulose during the last century, reflecting anthropogenic disturbance of atmospheric carbon dioxide, are thus overestimated. The likely explanation is that a proportion of the oxygen atoms are bonding with residual carbon in the reaction chamber to form carbon monoxide. The 'pyrolysis adjustment', proposed here, is based on combusting a stratified sub-sample of the pyrolysis results, across the full range of carbon isotope ratios, and using the paired results to define a regression equation that can be used to adjust all the pyrolysis measurements. In this study, subsamples of 30 combustion measurements produced adjusted chronologies statistically indistinguishable from those produced by combusting every sample. This methodology allows simultaneous measurement of the stable isotopes of carbon and oxygen using high-temperature pyrolysis, reducing the amount of sample required and the analytical costs of measuring them separately.

A trophic pathway from biogenic methane supports fish biomass in a temperate lake ecosystem

Although some primary consumers such as chironomid larvae are known to exploit methane‐derived carbon via microbial consortia within aquatic food webs, few studies have traced the onward transfer of such carbon to their predators. The ruffe Gymnocephalus cernuus is a widespread benthivorous fish which feeds predominantly on chironomid larvae and is well adapted for foraging at lower depths than other percids. Therefore, any transfer of methanogenic carbon to higher trophic levels might be particularly evident in ruffe. We sampled ruffe and chironomid larvae from the littoral, sub‐littoral and profundal areas of Jyväsjärvi, Finland, a lake which has previously been shown to contain chironomid larvae exhibiting the very low stable carbon isotope ratios indicative of methane exploitation. A combination of fish gut content examination and stable isotope analysis was used to determine trophic linkages between fish and their putative prey. Irrespective of the depth from which the ruffe were caught, their diet was dominated by chironomids and pupae although the proportions of taxa changed. Zooplankton made a negligible contribution to ruffe diet. A progressive decrease in δ13C and δ15N values with increasing water column depth was observed for both chironomid larvae and ruffe, but not for other species of benthivorous fish. Furthermore, ruffe feeding at greater depths were significantly larger than those feeding in the littoral, suggesting an ontogenetic shift in habitat use, rather than diet, as chironomids remained the predominant prey item. The outputs from isotope mixing models suggested that the incorporation of methane‐derived carbon to larval chironomid biomass through feeding on methanotrophic bacteria increased at greater depth, varying from 0% in the littoral to 28% in the profundal. Using these outputs and the proportions of littoral, sub‐littoral or profundal chironomids contributing to ruffe biomass, we estimated that 17% of ruffe biomass in this lake was ultimately derived from chemoautotrophic sources. Methanogenic carbon thus supports considerable production of higher trophic levels in lakes.

Survey for Li-rich K giants

AbstractWe present results from an ongoing survey of searching Li-rich K giants among low mass giants along the Red Giant Branch (RGB). A sample of 2500 stars with accurate astrometry have been selected from Hipparcos catalogue covering both the RGB luminosity bump and the red clump regions on the HR diagram. Lithium abundances have been determined for half of the sample from low resolution spectra using line depth ratio method. Results confirm the rarity of Li-rich K giants, just under 1%, in the solar neighbourhood. This study increased the total number of known Li-rich K giants by a factor of two. The analysis of high resolution spectra of candidate Li-rich K giants showed that the K giant HD 77361 is highly enriched in lithium (log ϵ(Li) = 3.82) and at the same time has anomalously low carbon isotopic ratio (12C/13C = 4.3). The results put important constraints on the theoretical modelling of the stellar structure and the mixing process, particularly, of the K giants.

The chemical composition of carbon stars. The R-type stars

The aim of this work is to shed some light on the problem of the formation of carbon stars of R-type from a detailed study of their chemical composition. We use high-resolution and high signal-to-noise optical spectra of 23 R-type stars selected from the Hipparcos catalogue. The chemical analysis is made using spectral synthesis in LTE and state-of-the-art carbon-rich spherical model atmospheres. We derive their CNO content (including the carbon isotopic ratio), average metallicity, lithium, and light (Sr, Y, Zr) and heavy (Ba, La, Nd, Sm) s-element abundances. The observed properties of the stars (galactic distribution, kinematics, binarity, photometry and luminosity) are also discussed. Our analysis shows that late-R stars are carbon stars with identical chemical and observational characteristics than the normal (N-type) AGB carbon stars. We confirm the results of the sole previous abundance analysis of early-R stars by Dominy (1984, ApJS, 55, 27), namely: they are carbon stars with near solar metallicity showing enhanced nitrogen, low carbon isotopic ratios and no s-element enhancements. In addition, we have found that early-R stars have Li abundances larger than expected for post RGB tip giants. We also find that a significant number (aprox. 40 %) of the early-R stars in our sample are wrongly classified, being probably classical CH stars and normal K giants. In consequence, we suggest that the number of true R stars is considerably lower than previously believed. We briefly discuss the different scenarios proposed for the formation of early-R stars. The mixing of carbon during an anomalous He-flash is favoured, although no physical mechanism able to trigger that mixing has been found yet. The origin of these stars still remains a mystery.

Methyl chloride and isoprene emissions from tropical rain forest in Southeast Asia

Methyl chloride (CH3Cl) fluxes were investigated at leaf and forest‐canopy scales in tropical forests in Malaysia. Screening of CH3Cl‐emitting species showed that 21% of 117 tree species were CH3Cl emitters; the percentage was markedly higher for dipterocarps (66%) than non‐dipterocarps (6%). The dipterocarp‐derived CH3Cl was characterized by high emissions (median: 0.03 μg g−1 h−1) and low stable carbon isotope ratios (mean: −88.9 ± 11.0‰). Measurements of CH3Cl above the canopy showed a slight decrease in the mixing ratios with increasing height. These values were used to estimate the canopy‐scale flux of about 14 μg m−2 h−1, comparable to that extrapolated from the leaf‐scale emissions. Using the canopy‐scale flux, global CH3Cl emission by tropical forests was estimated to be 1.3 Tg yr−1, representing approximately 30% of the global emissions. Above‐canopy measurements were also made for isoprene, with a mean flux of 1.2 mg m−2 h−1.

AGB stars of the intermediate-age LMC cluster NGC 1846

Aims: We investigate the change in the surface abundance of $^{12}$C during the evolution along the AGB, aiming to constrain third dredge-up models. Methods: High-resolution, near-infrared spectra of a sample of AGB stars in the LMC cluster NGC 1846 were obtained. A cluster sample ensures a high level of homogeneity with respect to age, metallicity, and distance. The C/O ratio and the ratio of $^{12}$C/$^{13}$C were measured and compared with our evolutionary models. Results: For the first time, we show the evolution of the C/O and $^{12}$C/$^{13}$C ratios along a cluster AGB. Our findings allow us to check the reliability of the evolutionary models and, in particular, the efficiency of the third dredge up. The increase in both C/O and $^{12}$C/$^{13}$C in the observed O-rich stars is reproduced by the models well. However, the low carbon isotopic ratios of the two C-stars in our sample indicate the late occurrence of moderate extra mixing. The extra mixing affects the most luminous AGB stars and is capable of increasing the abundance of $^{13}$C, while leaving unchanged the C/O ratio, which has been fixed by the cumulative action of several third dredge-up episodes. We find indications that the F abundance also increases along the AGB, supporting an in situ production of this element.

Low carbon isotope ratios in apatite: An unreliable biomarker in igneous and metamorphic rocks

Carbon isotope ratios of apatite have been used to interpret the source of carbon in magmas and metamorphic fluids, using the assumption that carbon isotope fractionations between phases are small in igneous and metamorphic systems. Measured carbon isotope fractionations between co-existing apatite and calcite from igneous, metaigneous, and metasedimentary rocks are large and variable (Δ 13C = 2.3 to 20.8‰), reflecting variability in δ 13C(Ap) sampled by combustion. This result indicates that carbon isotopes in apatite sampled by common techniques (combustion, ion microprobe, step-heating) do not have a straightforward interpretation. These data suggest that the low- δ 13C values in apatite that have previously been used as indicators of biological activity may be the result of the carbon isotope fractionation systematics of apatite, rather than a reflection of incorporation of organic carbon. This unusual fractionation behavior may require reconsideration of the significance of low- δ 13C carbonaceous inclusions in apatite from ≥ 3.8 Ga metamorphic rocks from Akilia Island, Greenland.

Basin geochemistry and isotopic ratios of fishes and basal production sources in four neotropical rivers

Abstract – We analysed stable carbon and nitrogen isotopic ratios of dissolved inorganic carbon (DIC), plants, detritus and fishes to estimate the relative importance of dominant production sources supporting food webs of four Venezuelan rivers with divergent geochemical and watershed characteristics. Based on samples taken during the dry season at each site, fishes from two nutrient‐poor, blackwater rivers had significantly lower δ13C values (mean = −31.4‰ and −32.9‰) than fishes from more productive clearwater and whitewater rivers (mean = −25.2‰ and −25.6‰ respectively). Low carbon isotopic ratios of fishes from blackwaters were likely influenced by low δ13C of DIC assimilated by aquatic primary producers. Although floodplains of three savanna rivers supported high biomass of C4 grasses, relatively little carbon from this source appeared to be assimilated by fishes. Most fishes in each system assimilated carbon derived mostly from a combination of microalgae and C3 macrophytes, two sources with broadly overlapping carbon isotopic signatures. Even with this broad overlap, several benthivorous grazers from blackwater and whitewater rivers had isotopic values that aligned more closely with algae. We conclude that comparative stable isotopic studies of river biota need to account for watershed geochemistry that influences the isotopic composition of basal production sources. Moreover, isotopic differences between river basins can provide a basis for discriminating spatial and temporal variation in the trophic ecology of fishes that migrate between watersheds having distinct geochemical characteristics.

The “Schistes carton” of Quercy (Tarn, France): a lithological signature of a methane hydrate dissociation event in the Early Toarcian. Implications for correlations between Boreal and Tethyan realms

Abstract The geochemical events (negative shifts in δ13C and δ18O, and Mn peak) associated with the “Schistes carton” of Quercy (SW France) do not appear to be due only to lithological variations and a differential diagenesis. They correspond to the Lower Toarcian global event and seem to be connected to a destabilization phase of gas hydrates. During its oxidation by seawater, the release of methane gas with a very low carbon isotopic ratio (− 60%) led to the production of CO2 and carbonates with a negative δ13C. The consumption of oxygen in the seawater resulted in conditions that were first dysoxic and then anoxic. The reduction of burrowing and bioturbation associated with this oxidation resulted in the laminated appearance of the “Schistes carton”. The decrease in the oxygen content led to a decrease in MnO2 microparticles present in the water column and sediments. This created a complementary source of Mn2+ that was incorporated into the carbonates produced during this event. Furthermore, an increase in the average seawater temperature (δ18O) appears associated with this event. Finally, the apparent diachronism of geochemical events in the Boreal and the Tethyan realms is discussed.

The mid-Oxfordian (Late Jurassic) positive carbon-isotope excursion recognised from fossil wood in the British Isles

The carbon-isotope ratios of fossil wood have recently been confirmed as a proxy for changes in the isotopic composition of palaeoatmospheres. Carbon-isotope data from fossil wood samples collected from the Jurassic (Oxfordian) Staffin Shale Formation on the Isle-of-Skye, Scotland (Boreal/Sub-Boreal ammonite zonation) reveal a long-term positive carbon-isotope excursion of at least 3‰. This excursion reaches a maximum in the mid-Oxfordian, and closely matches the carbon-isotope ratios previously reported from belemnites collected from the same section and carbon-isotope data from carbonates in other European sections. This confirms that the mid-Oxfordian positive carbon-isotope excursion affected the total exchangeable carbon reservoir. Fossilised wood samples collected at a higher stratigraphic resolution, but over a shorter interval from the Corallian Group in Dorset, England ( antecedens, parandieri and cautisnigrae subzones; NW European ammonite zonation) show considerable scatter in their carbon-isotope ratios, and no trends are discernable. The combined Isle-of-Skye and Dorset dataset shows that the long-term Oxfordian positive carbon-isotope trend coincides with a long-term relative sea-level change, and that the most positive carbon-isotope ratios occur across the plicatilis–transversarium biozonal boundary (Sub-Mediterranean ammonite zonation). This implies that the carbon-isotope excursion was not caused by the well-documented rise in sea-level in the transversarium Zone. Although very low carbon-isotope ratios from fossil wood samples are recorded from the Nodular Rubble Member ( parandieri Subzone) of Dorset, there is not a sufficiently coherent signal to ascribe these values to the gas–hydrate dissociation event previously hypothesized from the carbon-isotope ratios of Tethyan marine carbonates. A microscopal analysis of the charcoalified debris from the Staffin Shale Formation indicates a prevalence of the wood genus Cupressinoxylon, derived from a cheirolepidiaceaen conifer.