13C-depleted Carbon Research Articles

Investigation of the ‘canopy effect’ in the isotope ecology of temperate woodlands

Anomalously 13C-depleted carbon stable isotope values from closed forest ecosystems have been termed the ‘canopy effect’. Originally this was ascribed to recycling of depleted carbon from forest floor decomposition of organic material, although others have suggested that it is equally likely to be due to variations in leaf-level processes in response to increased shade. This depletion in the heavier carbon isotope is passed on to woodland herbivores feeding within the forest environments. A similar isotopic depletion has also been reported in the archaeological literature from more open temperate woodland settings, but no measurements have been made on the plants at the base of the food chain in order to quantify the effect. In this study we attempt this by examining the carbon and nitrogen stable isotopic values of different species of grasses from a range of open to closed habitat settings within Wytham Wood, Oxfordshire, UK. We find a strong relationship between carbon isotopic depletion of plant tissue and lowered light intensity with an up to 5‰ shift between grass grown in open and closed locations. In order to follow this up the food chain, we also report data on wool from sheep grazing in open pastures near the Wood, and on fallow deer living within the woodland, but which turn out not to show a strong canopy effect, probably related to their feeding strategies. We conclude that there is indeed a strong ‘canopy effect’ in temperate woodland, probably related to differential light levels, but that not all apparently woodland-dwelling mammals show such an effect. We also show considerable isotopic variation at the base of the food chain, which should counsel caution when attempting to interpret dietary isotopes using mixing models.

Peridotitic and websteritic diamondites provide new information regarding mantle melting and metasomatism induced through the subduction of crustal volatiles

Diamondites are mantle xenoliths comprised of polycrystalline diamond intergrown with garnet and minor clinopyroxene. Diamondites have some geochemical characteristics distinct from monocrystalline diamonds. Examples include 13C-depletion with modal δ13C value at −18‰ containing a high abundance of websteritic garnets (73%). This is in contrast to monocrystalline diamonds that show a strong mean δ13C value at −5‰ and low abundance of websteritic inclusions (2%). At present, geochemical studies focusing on diamondites are lacking, relative to coated and monocrystalline diamond. As a consequence, there exists a substantial volume of abundant mantle material that has been largely overlooked. We have determined the coupled δ13C–δ15N values and N-concentrations for 20 samples of mantle diamondite. Although their provenance is uncertain, these diamondites are thought to originate from Southern Africa because the major and rare Earth element (REE) compositions for the garnets are consistent with other Southern African diamondites.The coupled δ13C–δ15N values, N-concentrations in the diamond and REE patterns for the garnets we conclude that the source of the 13C-depleted carbon and 15N-enriched nitrogen is crustal in origin. This is by way of recycling subducted oceanic lithosphere beneath a stable craton, possibly the Kaapvaal craton in southern Africa. The peridotitic and websteritic garnet intergrowths have REE patterns similar to eclogitic garnets and we propose their petrogenesis due to mixing between a volatile saturated eclogitic melt and mantle peridotite. We propose that diamondites represent distinct diamond-forming event(s) related to mantle melting in the sub-cratonic mantle. Diamondite-formation events are proposed to be unrelated to most monocrystalline and coated diamonds formed by metasomatic processes involving little to no mantle melting.

Benthic ostracode δ13C as sensor for early Holocene establishment of modern circulation patterns in Central Europe

Shells from adult specimen of the benthic ostracodes Limnocytherina sanctipatricii and Leucocythere mirabilis selected from a 8.7 m long piston core provide continuous stable oxygen and carbon records for the past approximately 16 ka. Oxygen isotopes from both species show identical values and track the general North Atlantic and European temperature history since deglaciation in great detail. Values of ostracode δ18O values suggest that about 16 cal ka the average annual air temperatures were about 11 °C colder than today. Carbon isotopic values from both species of ostracodes are similar during the Lateglacial and early Holocene, and show an overall decrease from −4‰ to −7‰ that is probably related to an increase in photosynthetic productivity in the water column, as suggested by an increase in organic carbon, delivering 13C-depleted organic matter to the bottom waters (carbon pump). About 9 cal ka only L. mirabilis δ13C values decreased about −2.5‰ within 300 years. Higher δ13C variability and ecological evidence suggests that L. mirabilis represents a summer signal, whereas L. sanctipatricii displays a more subdued annual average. After about 7 cal ka another −1.5% decrease for both species, accompanied by an increase in magnetic susceptibility, a decrease in carbonate content, and more positive bulk carbonate isotope values followed, suggesting higher detrital-clastic input into the lake.In order to provide a possible mechanism explaining the negative L. mirabilis δ13C-values, sediment pore water profiles of O2 and CH4 in short cores collected from sites distal to proximal to the Alpine Rhine River delta, were inspected. Sediments in cores from more proximal sites to the Rhine delta become anoxic at shallower sediment depth due to the decay of high allochthonous organic carbon input to the sediment, which greatly increases concentrations of methane in pore waters closer to the Rhine inflow. When methane is oxidized close to the sediment–water-interface, 13C-depleted carbon is added to pore water DIC that is then available for incorporation into ostracode shells. This mechanism suggests that about 9 cal ka the oxygen supply to the bottom waters, especially in summer, decreased. This stimulated methanogenesis close to the sediment–water-interface, and provided δ13C-depleted carbon to benthic dwellers. Independent evidence for methanogenesis is provided by the increase in concentration of tetrahymanol after about 9 cal ka coincident with the decrease in δ13C of L. mirabilis.We suggest that about 9 cal ka the northward retreat of the Northern Hemisphere Ice Sheets, and consequently the polar front, left the alpine region affected by a more oceanic climate, characterized by warmer winters as they occur today especially during the positive North Atlantic Oscillation Index phase. More frequently incomplete mixing of the water column may have shifted the decay of organic matter faster to anaerobic conditions in surficial sediments especially during summer. By about 7 cal ka the North Atlantic region had probably warmed sufficiently to increase precipitation in Central Europe and consequently detrital-clastic runoff to Lake Constance.

Stable carbon isotopes of invertebrate remains: do they reveal past methane release from lakes?

Lakes are a source of methane, an important greenhouse gas in the atmosphere. In order to understand increasing methane emissions in the present, it is important to study the variations of methane release during past periods of climate change. However, records of methane release from lakes over time scales longer than a few years are extremely rare. In this thesis a method is explored to reconstruct past methane availability in lakes based on the stable carbon isotope composition (delta 13C) of aquatic invertebrate remains. Methane-derived 13C-depleted carbon can be an alternative carbon source to plant-derived material for invertebrates in the sediment and water column of lakes, that can lead to markedly depleted delta 13C values in invertebrate tissues. Using culturing experiments, it was demonstrated that methane-derived carbon is incorporated into chironomid head capsules. Also, it was shown that chemical pre-treatments that are commonly used for sediment processing do not have a noticeable effect on delta 13C values of chironomid remains and that a minimum of 20 microgram chitinous material is required for reproducible delta 13C measurements. In study lakes in Sweden and Siberia, delta 13C values of chitinous remains of several invertebrate taxa in surface sediments were negatively correlated with diffusive methane fluxes. Strong and significant correlations are observed between diffusive methane fluxes and delta 13C of Chironomini and Daphnia remains. Similar correlations were also observed within two Swedish lakes, in which surface sediment cores were obtained along depth transects. Delta 13C values of Chironomini and Daphnia were lower in sections of the lake basin in which the sediments had higher methane release rates. This suggests that delta 13C in remains of several invertebrates, especially Chironomini and Daphnia can be indicative of methane availability in lakes. In contrast, Orthocladiinae and Ephemeroptera, always had relatively high delta 13C values, indicating a plant-derived carbon source. In a sediment record from a Siberian thermokarst lake, delta 13C values of the remains of Chironomini and Daphnia showed relatively large negative delta 13C shifts in warm periods (AD 850-1150 and since AD 1970) compared with delta 13C values of Orthocladiinae remains and bulk sediment. Based on the observed correlations between methane fluxes and delta 13C values of Chironomini and Daphnia in surface sediment samples, this suggests that more methane-derived carbon was available in warm periods compared with colder periods. The research in this thesis demonstrates the potential to use taxon-specific stable carbon isotopes analysis of invertebrate remains for qualitative reconstructions of methane availability in lakes. This new method can lead to a better understanding of lake methane emissions in relation to climate change

Large-Amplitude Variations in Carbon Cycling and Terrestrial Weathering during the Latest Paleocene and Earliest Eocene: The Record at Mead Stream, New Zealand

AbstractThe late Paleocene to early Eocene was marked by major changes in Earth surface temperature and carbon cycling. This included at least two, and probably more, geologically brief (<200-k.yr.) intervals of extreme warming, the Paleocene-Eocene thermal maximum (PETM) and the Eocene thermal maximum-2 (ETM-2). The long-term rise in warmth and short-term “hyperthermal” events have been linked to massive injections of 13C-depleted carbon into the ocean-atmosphere system and intense global climate change. However, the causes, environmental impact, and relationships remain uncertain because detailed and coupled proxy records do not extend across the entire interval of interest; we are still recognizing the exact character of the hyperthermals and developing models to explain their occurrence. Here we present lithologic and carbon isotope records for a 200-m-thick sequence of latest Paleocene–earliest Eocene upper slope limestone exposed along Mead Stream, New Zealand. New carbon isotope and lithologic anal...

The effect of atmospheric CO2 concentration on carbon isotope fractionation in C3 land plants

Because atmospheric carbon dioxide is the ultimate source of all land-plant carbon, workers have suggested that pCO2 level may exert control over the amount of 13C incorporated into plant tissues. However, experiments growing plants under elevated pCO2 in both chamber and field settings, as well as meta-analyses of ecological and agricultural data, have yielded a wide range of estimates for the effect of pCO2 on the net isotopic discrimination (Δδ13Cp) between plant tissue (δ13Cp) and atmospheric CO2 (δ13CCO2). Because plant stomata respond sensitively to plant water status and simultaneously alter the concentration of pCO2 inside the plant (ci) relative to outside the plant (ca), any experiment that lacks environmental control over water availability across treatments could result in additional isotopic variation sufficient to mask or cancel the direct influence of pCO2 on Δδ13Cp. We present new data from plant growth chambers featuring enhanced dynamic stabilization of moisture availability and relative humidity, in addition to providing constant light, nutrient, δ13CCO2, and pCO2 level for up to four weeks of plant growth. Within these chambers, we grew a total of 191 C3 plants (128 Raphanus sativus plants and 63 Arabidopsis thaliana) across fifteen levels of pCO2 ranging from 370 to 4200ppm. Three types of plant tissue were harvested and analyzed for carbon isotope value: above-ground tissues, below-ground tissues, and leaf-extracted nC31-alkanes. We observed strong hyperbolic correlations (R≥0.94) between the pCO2 level and Δδ13Cp for each type of plant tissue analyzed; furthermore the linear relationships previously suggested by experiments across small (10–350ppm) changes in pCO2 (e.g., 300–310ppm or 350–700ppm) closely agree with the amount of fractionation per ppm increase in pCO2 calculated from our hyperbolic relationship. In this way, our work is consistent with, and provides a unifying relationship for, previous work on carbon isotopes in C3 plants at elevated pCO2. The values for Δδ13Cp we determined in our ambient pCO2 chambers are consistent with the Δδ13Cp values measured in large modern datasets of plants growing within the Earth’s wettest environments, suggesting that it may be possible to reconstruct changes in paleo-pCO2 level from plants that grew in consistently wet environments, if δ13CCO2 value and initial pCO2 level can be independently quantified. Several implications arise for the reconstruction of water availability and water-use efficiency in both ancient and recent plant Δδ13Cp values across periods of changing pCO2 level. For example, the change in Δδ13Cp implied by our relationship for the rise in pCO2 concentration observed since 1980 is of the same magnitude (= ∼0.7‰) as the isotopic correction for changes in δ13CCO2 required by the input of 13C-depleted carbon to the atmosphere. For these reasons, only the portion of the terrestrial isotopic excursion that persists after accounting for changes in pCO2 concentration should be used for the interpretation of a change in paleo-environmental conditions.

A multiple sulfur and organic carbon isotope record from non-conglomeratic sedimentary rocks of the Mesoarchean Witwatersrand Supergroup, South Africa

Multiple sulfur isotope ratios (36S/34S/33S/32S) and organic carbon isotope ratios (13C/12C) were measured from 198 non-conglomeratic sedimentary samples that were collected from five deep diamond drill-cores that cover the majority of the ca. 2.96–2.82Ga Witwatersrand Supergroup. δ13Corg, δ34Spy and Δ33Spy values of the sample set range from −44.3 to −21.9‰, −3.7 to +16.5‰ and −4.0 to +1.9‰, respectively. These geochemical data vary relative to depositional facies (proximal marine, distal marine and fluvial-dominated) and tectonic setting (trailing margin and foreland basin).In the trailing margin setting of the ∼2.96Ga Hospital Hill Subgroup, the proximal marine depofacies is characterized by relatively high organic carbon contents (up to 0.9wt.%) and δ13Corg values around −28‰, in contrast to the distal marine depofacies that yields low organic carbon contents (0.01wt.%) and high δ13Corg values (up to −22‰). Both depofacies yield low sulfur contents (0.02wt.‰), a narrow range of δ34S values (∼+3±2‰) and positive Δ33S values (up to +1.9‰). This data is consistent with photoautotrophic carbon fixation in shallow marine environments and limited organic carbon production/preservation in deeper water settings due to longer transport distances and effective biological degradation (e.g., Fe-reducing microbes). Positive Δ33S values imply that sulfur was largely derived from a photochemical elemental sulfur reservoir. In the foreland basin tectonic setting of the ∼2.94Ga Government and ∼2.92Ga Jeppestown subgroups, shelf deposits associated with fluvial braidplain depofacies are characterized by 13C-depleted organic carbon (∼−44 to −38‰), relatively high sulfur contents (0.2–1.3wt.%), variable δ34S values (−3.7 to +16.5‰) and small negative Δ33S values (∼−0.4‰). These data suggest that the microbial community in the fluvial-dominated depofacies may have consisted of photoautotrophs, methanogens, anaerobic methanotrophs and sulfate reducers. Sulfate was derived from a variety of sources that include photochemical, crustal and marine sulfur reservoirs.The occurrence of three regionally persistent diamictite deposits in the Government Subgroup coincides with the onset of compressional tectonics and development of pyritic shales with highly 13C-depleted organic carbon, suggesting that an increase in continental sulfur flux and methane oxidation may have triggered the Mesoarchean glaciations (drawdown of H2 and CH4). However, the link between large Δ33S anomalies (−4.0 to +1.2‰) and diamictite suggests low levels of atmospheric oxygen and minimal dilution of photochemical signatures.

Evidence for past variations in methane availability in a Siberian thermokarst lake based on δ13C of chitinous invertebrate remains

Understanding past methane dynamics in arctic wetlands and lakes is crucial for estimating future methane release. Methane fluxes from lake ecosystems have increasingly been studied, yet only few reconstructions of past methane emissions from lakes are available. In this study, we develop an approach to assess changes in methane availability in lakes based on δ13C of chitinous invertebrate remains and apply this to a sediment record from a Siberian thermokarst lake. Diffusive methane fluxes from the surface of ten newly sampled Siberian lakes and seven previously studied Swedish lakes were compared to taxon-specific δ13C values of invertebrate remains from lake surface sediments to investigate whether these invertebrates assimilated 13C-depleted carbon typical for methane. Remains of chironomid larvae of the tribe Orthocladiinae that, in the study lakes, mainly assimilate plant-derived carbon had higher δ13C than other invertebrate groups. δ13C of other invertebrates such as several chironomid groups (Chironomus, Chironomini, Tanytarsini, and Tanypodinae), cladocerans (Daphnia), and ostracods were generally lower. δ13C of Chironomini and Daphnia, and to a lesser extent Tanytarsini was variable in the lakes and lower at sites with higher diffusive methane fluxes. δ13C of Chironomini, Tanytarsini, and Daphnia were correlated significantly with diffusive methane flux in the combined Siberian and Swedish dataset (r = −0.72, p = 0.001, r = −0.53, p = 0.03, and r = −0.81, p < 0.001, respectively), suggesting that δ13C in these invertebrates was affected by methane availability. In a second step, we measured δ13C of invertebrate remains from a sediment record of Lake S1, a shallow thermokarst lake in northeast Siberia. In this record, covering the past ca 1000 years, δ13C of taxa most sensitive to methane availability (Chironomini, Tanytarsini, and Daphnia) was lowest in sediments deposited from ca AD 1250 to ca AD 1500, and after AD 1970, coinciding with warmer climate as indicated by an independent local temperature record. As a consequence the offset in δ13C between methane-sensitive taxa and bulk organic matter was higher in these sections than in other parts of the core. In contrast, δ13C of other invertebrate taxa did not show this trend. Our results suggest higher methane availability in the study lake during warmer periods and that thermokarst lakes can respond dynamically in their methane output to changing environmental conditions.

Constraints on hyperthermals

The abrupt warming event 56 million years ago, known as the Palaeocene–Eocene Thermal Maximum (PETM), was associated with the large scale release of 13C-depleted carbon into the ocean–atmosphere system. In sedimentary records, the event is reflected by a negative carbon isotope excursion1. Cui et al. used a carbon-cycle model to estimate the rate of carbon release during the PETM. The model assumed that the onset of the carbon isotope excursion occurred over approximately 20,000 years, an estimate based on a cyclostratigraphic model. Here we highlight several issues that weaken the conclusions of Cui et al.

Effect of different wetness conditions on Sphagnum lipid composition in the Erxianyan peatland, central China

Abstract Samples of Sphagnum palustre and peat from the Erxianyan peatland, central China, were analyzed for lipids and their carbon isotopes to investigate how lipid distributions respond to hydrological change and to evaluate the importance of the contribution of microbial lipids to the peat moss. The lipids in samples collected from different hydrological settings in and around a pond and in the central part of the bog show clear variation along the hydrological gradient, with higher n-C23/n-C25 alkane ratio values and lower ACL (average chain length) values of long chain n-alkanes, n-fatty alcohols and n-fatty acids at the wetter sites. Although the relationship between the S. palustre lipids and the hydrological conditions can be partially overprinted in peat by an input from vascular plants, lipid ratios such as Paq and ACL can provide useful qualitative information about Sphagnum contributions. In addition, lipid composition and carbon isotope values provide information about microbial activity associated with S. palustre. The occurrence of a high abundance of 7-methylheptadecane in submerged S. palustre is an indication of cyanobacteria in the living peat moss. The relatively 13C-depleted carbon isotope values of the n-C23 alkane could result from the influence of symbiotic methanotrophs on the carbon available for assimilation by S. palustre.

Anaerobic oxidation of methane in hypersaline Messinian environments revealed by 13C-depleted molecular fossils

The Messinian sequence of evaporitic deposits in Italy includes authigenic carbonates that have been suggested to derive from the microbial degradation of organic compounds, but the biogeochemical mechanisms that led to their formation remained unknown. To unravel these mechanisms, 13 C-depleted carbonate rocks including native sulphur-bearing limestone (Calcare Solfifero) from two locations in Sicily and bedded limestone from the northern Apennines have been studied. Their δ 13 C values as low as − 49‰ reflect incorporation of carbon derived from the oxidation of methane, which was previously suggested to have been linked to bacterial sulphate reduction. Molecular fossils extracted from the limestones reveal that methane was indeed oxidized in an anaerobic process by archaea and sulphate-reducing bacteria. The observed biomarker patterns resemble those of methane-seep carbonates, which form as a consequence of the anaerobic oxidation of methane (AOM). AOM-specific, 13 C-depleted archaeal biomarkers such as PMI (δ 13 C: − 101 to − 75‰) as well as compounds derived from sulphate-reducing bacteria ( iso- and anteiso-fatty acids; δ 13 C as low as − 85‰) were identified in the Messinian carbonates. Although the biomarker results clearly point to AOM, the compound inventory also revealed distinct differences to patterns found at marine methane-seeps. For example, sn3-hydroxyarchaeol is in some samples the only hydroxyarchaeol present, something usually not found at seeps. Archaeol is less depleted in 13 C than PMI at most sites (δ 13 C: − 55 to − 30‰), pointing to the co-occurrence of methanogenic or halophilic archaea with archaea involved in AOM. (1) The presence of calcite pseudomorphs after lenticular gypsum, (2) 18 O-enrichment in carbonates, and (3) the biomarkers O-phytanyl -O-sesterterpanyl glycerolether (extended archaeol), tetrahymanol, and possibly phytanylglycerol monoethers as well as non-isoprenoidal macrocyclic glycerol diethers confirm that carbonate formation took place under evaporitic conditions. AOM has previously been shown to be inhibited in some brine pools on the modern seafloor. Our observations, however, demonstrate that AOM functions in hypersaline environments as well.

Seasonal increase of methane in sediment decreases δ13C of larval chironomids in a eutrophic shallow lake

Recent studies have shown that larval chironomids assimilate 13C-depleted carbon derived from biogenic methane by feeding on methane-oxidizing bacteria (MOB). The dietary contribution of MOB is known to be maximized in the autumn overturn period or winter in eutrophic dimictic lakes due to the increase of MOB biomass following the supply of oxygenated water, but in polymictic lakes, such seasonal variability has not been revealed. We investigated the seasonal patterns of larval δ13C and methane concentrations in the sediment of a eutrophic polymictic lake, Izunuma, Japan. Larval δ13C decreased in late summer and autumn. Methane concentrations above a 6 cm depth peaked in late summer or autumn, while those in the 10–11- and 20–21-cm layers peaked in October. Negative correlations between methane concentrations in the 5–6/10–11-cm layers and larval δ13C were found. This suggests that an increase in the supply of methane stimulated the activity of MOB in a polymictic lake, where water above the lake bottom rarely became anoxic because of frequent overturn, thus increasing the dietary contribution of MOB to larval chironomids.

Polar record of Early Jurassic massive carbon injection

The Toarcian Oceanic Anoxic Event (T-OAE) (ca. 182 Myr, Early Jurassic) represents one of the best-recognized examples of greenhouse warming, decreased seawater oxygenation and mass extinction. The leading hypothesis to explain these changes is the massive injection of thermogenic or gas hydrate-derived 13C-depleted carbon into the atmosphere, resulting in a > 3 per mil negative carbon isotope excursion (CIE), accelerated nutrient input and dissolved oxygen consumption in the oceans. Nevertheless, the lack of a precisely dated record of the T-OAE outside low latitudes has led to considerable debate about both its temporal and spatial extent and hence concerning its underlying causes. Here we present new isotopic and lithological data from three precisely dated N Siberian sections, which demonstrate that mass extinction and onset of strong oxygen-deficiency occurred near synchronously in polar and most tropical sites and were intimately linked to the onset of a marked 6‰ negative CIE recorded by bulk organic carbon. Rock Eval pyrolysis data from Siberia and comparisons with low latitudes show that the CIE cannot be explained by the extent of stratification of the studied basins or changes in organic matter sourcing and suggest that the negative CIE reflects rapid 13C-depleted carbon injection to all exchangeable reservoirs. Sedimentological and palynological indicators show that the injection coincided with a change from cold (abundant glendonites and exotic boulder-sized clasts) to exceptionally warm conditions (dominance of the thermophyllic pollen genus Classopollis) in the Arctic, which likely triggered a rapid, possibly partly glacioeustatic sea-level rise. Comparisons with low latitude records reveal that warm climate conditions and poor marine oxygenation persisted in continental margins at least 600 kyr after the CIE, features that can be attributed to protracted and massive volcanic carbon dioxide degassing. Our data reveal that the T-OAE profoundly affected Arctic climate and oceanography and suggest that the CIE was a consequence of global and massive 13C-depleted carbon injection.

Post-depositional origin of highly 13C-depleted carbonate in the Doushantuo cap dolostone in South China: Insights from petrography and stable carbon isotopes

Extremely negative carbon isotope values from the Doushantuo cap dolostone succession in the Yangtze Gorges, South China were interpreted as direct evidence of the hypothesis of methane hydrate destabilization during the Marinoan deglaciation. However, this suggestion remains uncertain due to the obscurity of the paragenetic sequence of carbonate minerals with diverse carbon isotopic compositions. Here, we conducted macroscopic and microscopic petrographic and carbon isotopic investigations of the cap dolostone succession at the Jiulongwan section in the Yangtze Gorges. Our results show that extreme δ 13C values down to − 44‰ exclusively occur in calcite, whereas δ 13C values for the host dolomite range mostly between − 4‰ and − 2‰, and clearly reveal that the host dolomite were locally dissolved and/or replaced by the calcite bearing highly 13C-depleted signals. This finding suggests that methane-oxidation activity as indicated by the strongly depleted δ 13C signals did not occur until after the cap dolostone deposition. Thus, the presence of the extremely negative δ 13C values could not be taken as evidence for the proposed methane hypothesis. Nevertheless, this conclusion is not contradictory to the scenario that massive releases of methane from permafrost hydrates during deglaciation, much prior to methane oxidation documented here, could drive substantial negative δ 13C shifts well exhibited by the Doushantuo cap dolostone and others around the world.

Down the Rabbit Hole: toward appropriate discussion of methane release from gas hydrate systems during the Paleocene-Eocene thermal maximum and other past hyperthermal events

Abstract. Enormous amounts of 13C-depleted carbon rapidly entered the exogenic carbon cycle during the onset of the Paleocene-Eocene thermal maximum (PETM), as attested to by a prominent negative carbon isotope (δ13C) excursion and deep-sea carbonate dissolution. A widely cited explanation for this carbon input has been thermal dissociation of gas hydrate on continental slopes, followed by release of CH4 from the seafloor and its subsequent oxidation to CO2 in the ocean or atmosphere. Increasingly, papers have argued against this mechanism, but without fully considering existing ideas and available data. Moreover, other explanations have been presented as plausible alternatives, even though they conflict with geological observations, they raise major conceptual problems, or both. Methane release from gas hydrates remains a congruous explanation for the δ13C excursion across the PETM, although it requires an unconventional framework for global carbon and sulfur cycling, and it lacks proof. These issues are addressed here in the hope that they will prompt appropriate discussions regarding the extraordinary carbon injection at the start of the PETM and during other events in Earth's history.

A hydrothermal origin for isotopically anomalous cap dolostone cements from south China

The release of methane into the atmosphere through destabilization of clathrates is a positive feedback mechanism capable of amplifying global warming trends that may have operated several times in the geological past. Such methane release is a hypothesized cause or amplifier for one of the most drastic global warming events in Earth history, the end of the Marinoan 'snowball Earth' ice age, ∼635 Myr ago. A key piece of evidence supporting this hypothesis is the occurrence of exceptionally depleted carbon isotope signatures (δ(13)C(PDB) down to -48‰; ref. 8) in post-glacial cap dolostones (that is, dolostone overlying glacial deposits) from south China; these signatures have been interpreted as products of methane oxidation at the time of deposition. Here we show, on the basis of carbonate clumped isotope thermometry, (87)Sr/(86)Sr isotope ratios, trace element content and clay mineral evidence, that carbonates bearing the (13)C-depleted signatures crystallized more than 1.6 Myr after deposition of the cap dolostone. Our results indicate that highly (13)C-depleted carbonate cements grew from hydrothermal fluids and suggest that their carbon isotope signatures are a consequence of thermogenic methane oxidation at depth. This finding not only negates carbon isotope evidence for methane release during Marinoan deglaciation in south China, but also eliminates the only known occurrence of a Precambrian sedimentary carbonate with highly (13)C-depleted signatures related to methane oxidation in a seep environment. We propose that the capacity to form highly (13)C-depleted seep carbonates, through biogenic anaeorobic oxidation of methane using sulphate, was limited in the Precambrian period by low sulphate concentrations in sea water. As a consequence, although clathrate destabilization may or may not have had a role in the exit from the 'snowball' state, it would not have left extreme carbon isotope signals in cap dolostones.

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ 13C were analyzed. Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ 13C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide. The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.

A New Zealand record of sea level rise and environmental change during the Paleocene–Eocene Thermal Maximum

The global warming associated with the Paleocene–Eocene Thermal Maximum (PETM) ca. 55.5 Myr ago is the most dramatic identified short-term temperature increase of the Cenozoic. One direct consequence of a warming world is a rise in sea level, due primarily to the thermal expansion of water as oceans warmed. The Kumara-2 core, South Island, New Zealand, spans the Paleocene/Eocene transition and provides a rare southern hemisphere continental margin record of the PETM. Lithology, palynology and compound-specific stable isotope compositions of higher plant leaf wax n-alkanes reveal a 4.85 m PETM and a carbon isotope excursion (CIE) of ca. − 4.5‰, larger than the − 2.5 to − 3.5‰ CIEs generally recorded by deep sea foraminifera. There is a shift from a terrestrial to a marine, potentially anoxic, sedimentary depositional environment at the base of the PETM, interpreted as being the result of a local sea level rise. Coincident with the onset of the CIE is the appearance of pollen associated with thermophilic conditions and the development of Nypa mangrove swamps. Moreover, there is a reorganisation of the angiosperm pollen assemblage during the PETM, and an initial increase in fern spores and decrease in gymnosperms. Crucially, all of these changes occur below the horizon characterised by the most negative δ 13C values, suggesting that: 1) the recorded negative excursion of 4.5‰ may indeed reflect the shift in atmospheric CO 2 isotopic composition; and 2) that the large input of 13C-depleted carbon into the ocean–atmosphere system was not geologically instantaneous, with at least some of the added carbon lagging warming, sea level rise and vegetation change. Furthermore, compound-specific hydrogen isotope analyses show a large degree of variability both directly before and during the CIE, suggesting that the PETM in New Zealand was characterised by complex and transient changes in the hydrological regime, similar to those reported in North America, the Arctic and Eastern Africa. Thus, the new PETM record from Kumara-2 reveals local climatic and biotic responses, driven by a combination of global warming and the consequential change in local depositional environment induced by sea level rise.

Mass Occurrences of the BrachiopodHalorellain Late Triassic Methane-Seep Deposits, Eastern Oregon

The temporally and geographically scattered Phanerozoic record of methane-seep deposits hampers reconstruction of the evolution of life in chemosynthesis-based ecosystems. Unlike modern, Cenozoic, and late Mesozoic seeps, many of the known older seep deposits are typified by assemblages with profuse rhynchonellide brachiopods. Late Triassic (Norian) limestone bodies in eastern Oregon are enclosed in deep-water strata, extend laterally for up to a few hundred meters, and contain the dimerelloid rhynchonellide Halorella in rock-forming quantities. The analysis of two large limestone bodies in the Rail Cabin Member of the Vester Formation exposed near Graylock Butte, Grant County, Oregon, fosters the reconstruction of the paleoenvironmental setting of these unusual Halorella deposits, resulting in the first recognition of Triassic methane-seep deposits. The faunal assemblage includes few fossils other than Halorella. Although occasionally found at seeps, the recognized nuculanids are not seep-endemic bivalves. A Nucinella-like bivalve and a possible permophorid bivalve were likely endemic to this chemosynthesis-based environment; related bivalves lived at Jurassic and Cretaceous seeps. The superabundant, mostly articulated brachiopod shells are enclosed in a variety of micrites, including peloidal to clotted micrite. Early fibrous cement, forming banded and botryoidal crystal aggregates, preferentially occurs at the margin of the large limestone bodies but is scarce overall. Peloidal to clotted micrite and banded and botryoidal cement are common constituents of methane-seep limestones. Their negative δ13C values as low as −36‰ reveal that carbonate formation was induced by the oxidation of methane. The presence of pyrobitumen (i.e., metamorphosed crude oil) in the limestones may indicate that the seepage fluids contained oil in addition to methane. Apart from the diagnostic 13C-depleted carbonate phases, mud injections recognized in one of the two limestone bodies also bear testament to former seepage activity.

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian–Oxfordian clayey formation of Bure (France)

The Callovian–Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ 34S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ 34S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ 34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/ 86Sr ratio of celestite (0.706872–0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ 18O consistent with a marine environment. Its δ 13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ 18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ 18O values (∼+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.