Termination of global warmth at the Palaeocene/Eocene boundary through productivity feedback

The onset of the Palaeocene/Eocene thermal maximum (about 55 Myr ago) was marked by global surface temperatures warming by 5-7 degrees C over approximately 30,000 yr (ref. 1), probably because of enhanced mantle outgassing and the pulsed release of approximately 1,500 gigatonnes of methane carbon from decomposing gas-hydrate reservoirs. The aftermath of this rapid, intense and global warming event may be the best example in the geological record of the response of the Earth to high atmospheric carbon dioxide concentrations and high temperatures. This response has been suggested to include an intensified flux of organic carbon from the ocean surface to the deep ocean and its subsequent burial through biogeochemical feedback mechanisms. Here we present firm evidence for this view from two ocean drilling cores, which record the largest accumulation rates of biogenic barium--indicative of export palaeoproductivity--at times of maximum global temperatures and peak excursion values of delta13C. The unusually rapid return of delta13C to values similar to those before the methane release and the apparent coupling of the accumulation rates of biogenic barium to temperature, suggests that the enhanced deposition of organic matter to the deep sea may have efficiently cooled this greenhouse climate by the rapid removal of excess carbon dioxide from the atmosphere.     

Geochemistry: biosignatures and abiotic constraints on early life

Ueno et al. contend that methane found in fluid inclusions within hydrothermally precipitated quartz in the Dresser Formation of western Australia (which is roughly 3.5 Gyr old) provides evidence for microbial methanogenesis in the early Archaean era. The authors discount alternative origins for this methane, suggesting that the range of delta(13)C(CH(4)) values that they record (-56 to -36 per thousand) is attributable to mixing between a primary microbial end-member with a delta(13)C(CH(4)) value of less than -56 per thousand and a mature thermogenic gas enriched in (13)C (about -36 per thousand). However, abiotic methane produced experimentally and in other Precambrian greenstone settings has (13)C-depleted delta(13)C(CH(4)) values, as well as Delta(13)C(CO(2)-CH(4)) relationships that encompass the range measured for the inclusions by Ueno et al. - which suggests that an alternative, abiotic origin for the methane is equally plausible. The conclusions of Ueno et al. about the timing of the onset of microbial methanogenesis might not therefore be justified.     

Uncovering the Neoproterozoic carbon cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter. Neoproterozoic carbonate records contain unusual and large negative isotopic anomalies within long periods (10-100 million years) characterized by δ(13)C in carbonate (δ(13)C(carb)) enriched to more than +5 per mil. Classically, δ(13)C(carb) is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments, which can be linked to oxygen accumulation through the stoichiometry of primary production. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of δ(13)C(carb) and δ(13)C in organic carbon (δ(13)C(org)) will covary, offset by the fractionation imparted by primary production. The documentation of several Neoproterozoic δ(13)C(carb) excursions that are decoupled from δ(13)C(org), however, indicates that other mechanisms may account for these excursions. Here we present δ(13)C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple δ(13)C(carb) excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret δ(13)C(carb) anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals.     

Astronomical pacing of methane release in the Early Jurassic period

A pronounced negative carbon-isotope (delta13C) excursion of approximately 5-7 per thousand (refs 1-7) indicates the occurrence of a significant perturbation to the global carbon cycle during the Early Jurassic period (early Toarcian age, approximately 183 million years ago). The rapid release of 12C-enriched biogenic methane as a result of continental-shelf methane hydrate dissociation has been put forward as a possible explanation for this observation. Here we report high-resolution organic carbon-isotope data from well-preserved mudrocks in Yorkshire, UK, which demonstrate that the carbon-isotope excursion occurred in three abrupt stages, each showing a shift of -2 per thousand to -3 per thousand. Spectral analysis of these carbon-isotope measurements and of high-resolution carbonate abundance data reveals a regular cyclicity. We interpret these results as providing strong evidence that methane release proceeded in three rapid pulses and that these pulses were controlled by astronomically forced changes in climate, superimposed upon longer-term global warming. We also find that the first two pulses of methane release each coincided with the extinction of a large proportion of marine species.     

Latitudinal variations in plankton delta 13C: implications for CO2 and productivity in past oceans

The stable-carbon isotopic composition of marine organic material has varied significantly over geological time, and reflects significant excursions in the isotopic fractionation associated with the uptake of carbon by marine biota. For example, low 13C/12C in Cretaceous sediments has been attributed to elevated atmospheric (and hence oceanic) CO2 partial pressures. A similar depletion in 13C present-day Antarctic plankton has also been ascribed to high CO2 availability. We report, however, that this high-latitude isotope depletion develops at CO2 partial pressures (pCO2 levels) that are often below that of the present atmosphere (340 microatmospheres) , and usually below that of equatorial upwelling systems (> 340 microatmospheres). Nevertheless, because of the much lower water temperatures and, hence, greater CO2 solubility at high latitude, the preceding pCO2 measurements translate into Antarctic surface-water CO2 (aq) concentrations that are as much as 2.5 times higher than in equatorial waters. We calculate that an oceanic pCO2 level of > 800 microatmospheres (over twice the present atmospheric pCO2) in a warmer low-latitude Cretaceous ocean would have been required to produce the plankton 13C depletion preserved in Cretaceous sediments.     

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.     

Changes in carbon dioxide during an oceanic anoxic event linked to intrusion into Gondwana coals

The marine sedimentary record exhibits evidence for episodes of enhanced organic carbon burial known as 'oceanic anoxic events' (OAEs). They are characterized by carbon-isotope excursions in marine and terrestrial reservoirs and mass extinction of marine faunas. Causal mechanisms for the enhancement of organic carbon burial during OAEs are still debated, but it is thought that such events should draw down significant quantities of atmospheric carbon dioxide. In the case of the Toarcian OAE (approximately 183 million years ago), a short-lived negative carbon-isotope excursion in oceanic and terrestrial reservoirs has been interpreted to indicate raised atmospheric carbon dioxide caused by oxidation of methane catastrophically released from either marine gas hydrates or magma-intruded organic-rich rocks. Here we test these two leading hypotheses for a negative carbon isotopic excursion marking the initiation of the Toarcian OAE using a high-resolution atmospheric carbon dioxide record obtained from fossil leaf stomatal frequency. We find that coincident with the negative carbon-isotope excursion carbon dioxide is first drawn down by 350 +/- 100 p.p.m.v. and then abruptly elevated by 1,200 +/- 400 p.p.m.v, and infer a global cooling and greenhouse warming of 2.5 +/- 0.1 degrees C and 6.5 +/- 1 degrees C, respectively. The pattern and magnitude of carbon dioxide change are difficult to reconcile with catastrophic input of isotopically light methane from hydrates as the cause of the negative isotopic signal. Our carbon dioxide record better supports a magma-intrusion hypothesis, and suggests that injection of isotopically light carbon from the release of thermogenic methane occurred owing to the intrusion of Gondwana coals by Toarcian-aged Karoo-Ferrar dolerites.     

High-resolution carbon isotope record for the Paleocene-Eocene thermal maximum from the Nanyang Basin,Central China

The Paleocene-Eocene thermal maximum (PETM) was a transient episode of global warming, associated with massive atmospheric greenhouse gas input that occurred at the Paleocene/Eocene boundary. Biostratigraphic and isotope stratigraphic studies indicate that the PETM event is well documented in the marl deposits of the Yuhuangding section in the Nanyang Basin, Central China, with a carbon isotope negative excursion of ~6.1‰ within 19-m-thick marl deposits. This is the highest resolution record of the PETM so far found in the world. The PETM event was triggered within 2-cm-thick marl sediments, with a decrease of δ¹³C (stable carbon isotope ratio) from –3.2‰ to –5.2‰, suggesting a massive methane hydrate release for a transient period that was possibly caused by a catastrophic event. A comparison between marine and terrestrial records indicates a “Three-Phase Model” for the PETM event. Initially there is a rapid negative excursion in the δ¹³C record, followed by a slowly decreasing trend, and then a gradual positive recovery, corresponding respectively to a rapid dissociation of oceanic methane hydrate, followed by a slow release of methane and then the consumption of the released methane.     

Arctic Ocean: hydrothermal activity on Gakkel Ridge

In the hydrothermal circulation at mid-ocean ridges, sea water penetrates the fractured crust, becomes heated by its proximity to the hot magma, and returns to the sea floor as hot fluids enriched in various chemical elements. In contradiction to earlier results that predict diminishing hydrothermal activity with decreasing spreading rate, a survey of the ultra-slowly spreading Gakkel Ridge (Arctic Ocean) by Edmonds et al. and Michael et al. suggests that, instead of being rare, the hydrothermal activity is abundant--exceeding by at least a factor of two to three what would be expected by extrapolation from observation on faster spreading ridges. Here we use helium-3 (3He), a hydrothermal tracer, to show that this abundance of venting sites does not translate, as would be expected, into an anomalous hydrothermal 3He output from the ridge. Because of the wide implications of the submarine hydrothermal processes for mantle heat and mass fluxes to the ocean, these conflicting results call for clarification of the link between hydrothermal activity and crustal production at mid-ocean ridges.     

CO2 and the end-Triassic mass extinction.

The end of the Triassic period was marked by one of the largest and most enigmatic mass-extinction events in Earth's history and, with few reliable marine geochemical records, terrestrial sediments offer an important means of deciphering environmental changes at this time. Tanner et al. describe an isotopic study of Mesozoic fossil soils which suggests that the atmospheric concentration of carbon dioxide (pCO2) across the Triassic-Jurassic boundary was relatively constant (within 250 p.p.m.v.), but this is inconsistent with high-resolution evidence from the stomatal characters of fossil leaves. Here I show that the temporal resolution of the fossil-soil samples may have been inadequate for detecting a transient rise in pCO2. I also show that the fossil-soil data are consistent with a large increase in pCO2 across the Triassic-Jurassic boundary when variations in the stable carbon isotope (denoted as delta13C) in terrestrial plant leaves are taken into account. These factors suggest that the linkage between pCO2, global warming and the end-Triassic mass extinction remains intact.     

Aerobic respiration in the Archaean?

The Earth's atmosphere during the Archaean era (3,800-2,500 Myr ago) is generally thought to have been anoxic, with the partial pressure of atmospheric oxygen about 10(-12) times the present value. In the absence of aerobic consumption of oxygen produced by photosynthesis in the ocean, the major sink for this oxygen would have been oxidation of dissolved Fe(II). Atmospheric oxygen would also be removed by the oxidation of biogenic methane. But even very low estimates of global primary productivity, obtained from the amounts of organic carbon preserved in Archaean rocks, seem to require the sedimentation of an unrealistically large amount of iron and the oxidation of too much methane if global anoxia was to be maintained. I therefore suggest that aerobic respiration must have developed early in the Archaean to prevent a build-up of atmospheric oxygen before the Proterozoic. An atmosphere that contained a low (0.2-0.4%) but stable proportion of oxygen is required.     

Benthic foraminiferal δ~(13)C minimum events in the southeastern Okhotsk Sea over the last 180 ka

A total of six d13C minimum events,i.e.,VI,V,IV,III,II,and I,were observed via a stable carbon and oxygen isotope analysis of infaunal benthic foraminifera Uvigerina spp.in gravity core OS03-1 in the southeastern Okhotsk Sea over the last 180 ka.These events occurred at112–109,102–90,85–76,57–54,44–40,and 17–10 ka BP.The largest negative excursions reached 2.5%in event V and were greater than 1%in the other events.We proposed that all d13C minimum events were caused by the increase in sea surface water productivity,the weakened formation of Okhotsk Sea intermediate water,and the enhancement of the oxygen minimum zone.The negative excursions were unaffected by methane hydrate destabilization and subsequent methane release based on the results obtained by using archaeal lipid markers.     

Methanotrophic symbionts provide carbon for photosynthesis in peat bogs

Wetlands are the largest natural source of atmospheric methane, the second most important greenhouse gas. Methane flux to the atmosphere depends strongly on the climate; however, by far the largest part of the methane formed in wetland ecosystems is recycled and does not reach the atmosphere. The biogeochemical controls on the efficient oxidation of methane are still poorly understood. Here we show that submerged Sphagnum mosses, the dominant plants in some of these habitats, consume methane through symbiosis with partly endophytic methanotrophic bacteria, leading to highly effective in situ methane recycling. Molecular probes revealed the presence of the bacteria in the hyaline cells of the plant and on stem leaves. Incubation with (13)C-methane showed rapid in situ oxidation by these bacteria to carbon dioxide, which was subsequently fixed by Sphagnum, as shown by incorporation of (13)C-methane into plant sterols. In this way, methane acts as a significant (10-15%) carbon source for Sphagnum. The symbiosis explains both the efficient recycling of methane and the high organic carbon burial in these wetland ecosystems.     

Unicellular C4 photosynthesis in a marine diatom

Nearly 50 years ago, inorganic carbon was shown to be fixed in microalgae as the C3 compound phosphoglyceric acid. The enzyme responsible for C3 carbon fixation, ribulose-1,5-bisphosphate carboxylase (Rubisco), however, requires inorganic carbon in the form of CO2 (ref. 2), and Rubisco enzymes from diatoms have half-saturation constants for CO2 of 30-60 microM (ref. 3). As a result, diatoms growing in seawater that contains about 10 microM CO2 may be CO2 limited. Kinetic and growth studies have shown that diatoms can avoid CO2 limitation, but the biochemistry of the underlying mechanisms remains unknown. Here we present evidence that C4 photosynthesis supports carbon assimilation in the marine diatom Thalassiosira weissflogii, thus providing a biochemical explanation for CO2-insensitive photosynthesis in marine diatoms. If C4 photosynthesis is common among marine diatoms, it may account for a significant portion of carbon fixation and export in the ocean, and would explain the greater enrichment of 13C in diatoms compared with other classes of phytoplankton. Unicellular C4 carbon assimilation may have predated the appearance of multicellular C4 plants.     

Dual modes of the carbon cycle since the Last Glacial Maximum

The most conspicuous feature of the record of past climate contained in polar ice is the rapid warming which occurs after long intervals of gradual cooling. During the last four transitions from glacial to interglacial conditions, over which such abrupt warmings occur, ice records indicate that the CO2 concentration of the atmosphere increased by roughly 80 to 100 parts per million by volume. But the causes of the atmospheric CO2 concentration increases are unclear. Here we present the stable-carbon-isotope composition (delta 13 CO2) of CO2 extracted from air trapped in ice at Taylor Dome, Antarctica, from the Last Glacial Maximum to the onset of Holocene times. The global carbon cycle is shown to have operated in two distinct primary modes on the timescale of thousands of years, one when climate was changing relatively slowly and another when warming was rapid, each with a characteristic average stable-carbon-isotope composition of the net CO2 exchanged by the atmosphere with the land and oceans. delta 13 CO2 increased between 16.5 and 9 thousand years ago by slightly more than would be estimated to be caused by the physical effects of a 5 degrees C rise in global average sea surface temperature driving a CO2 efflux from the ocean, but our data do not allow specific causes to be constrained.     

Reconstruction of surface ocean water <Emphasis Type="Italic">p</Emphasis>CO<Subscript>2</Subscript>(aq) in Nansha area,the South China Sea during the last 30 ka

The reconstruction of pCO2 in the tropic ocean is one of the most important issues to understand global climatic changes.In this study,the high-resolution stratigraphic analysis of core 17962 was conducted,which is Iocated in the southern South China Sea(SCS).The contents of sedimentary organic matter,the stable carbon isotopic composition of sedimentary organic matter,and the δ^13C values of black carbon and terrigenons n-alkanes were determined.And the δ^13Cwc value of carbon derived from aquatic was calculated.On the basis of δ^13Corg-pCO2equation proposed by Popp et al.(1989),we estimated the pCO2 in the Nansha area,SCS,since the last glaciation using δ^13Cwc instead of δ^13Corg.The results show that the average pCO2 was estimated at 240 ppm V during the last glaciation,and at 320ppm V in the Holocene.A comparison of surface sea pCO2 with the atmosphere CO2 recorded in the Vostok ice core,indicates that CO2 in surface water of the southern SCS could emit into atmosphere during the last 30ka.     

Ediacaran oxidation and biotic evolution

The link between the radiation of various lineages of eukaryotes in the latest Proterozoic and massive environmental changes--oxygenation, global ice ages and bolide impact--is the focus of much research interest. Fike et al. use carbon and sulphur isotope-chemostratigraphic data from Oman to propose three stages of oxidation in the Ediacaran oceans, and link the second and third stages to eukaryote diversification. The second stage, signalled by strongly 13C-depleted sedimentary carbonates (the 'Shuram excursion'), is believed to result from oxidation of a large, deep-ocean reservoir of organic carbon. Fike et al. use our data to assert that a correlative carbon isotope excursion in Australia coincided with the initial diversification of acanthomorphic acritarchs. Peak diversity is claimed to have coincided with subsequent deposition of 13C-enriched carbonate and the third oxidation stage. However, the authors seem to have misinterpreted our data, which instead indicate that diversification significantly preceded the Shuram excursion; this weakens their argument for a link between the inferred oxidation events and eukaryote evolution.     

Carbon isotopic record from Upper Devonian carbonates at Dongcun in Guilin,southern China,supporting the worldwide pattern of carbon isotope excursions during Frasnian-Famennian transition

Carbon isotopic composition of carbonates and or-ganic matter in sediments has been a powerful tool for deducing perturbations in the global carbon cycle which, in many cases, is observed together with the occurrence of biological mass extinctions[1]. The Frasnian-Famennian (F-F) mass extinction[2,3], so-called F-F event or bio-crisis, has been recognized as one of the five major bioevents of Phanerozoic time[4—7], and more than 60% of all Frasnian genera were eliminated[3,11]. This event …     

Research progress in studies on the coalbed gas geochemistry

The current situation of geochemical studies on coalbed gas is reviewed in this paper. Generally, coalbed gas is compositionally dominated by methane with δ¹³C₁ values ranging approximately from -80‰ to -10‰. However, few isotopic studies have been carried out on other components of coalbed gas except for hydrogen and carbon dioxide, whose δD_CH4 values available for utilization vary from -333‰ to -117‰, and δ¹³C_CO2 values from -29.4‰ to +18.6‰. Two major types of coalbed gas, thermogenic gas and secondary biogenic gas, have been identified, and there are also some other classification criteria. Compared with conventional natural gases, coalbed gas has a wide distribution range of δ¹³C₁ and δ¹³C_CO2 values, especially possessing some extremely heavy values. Current problems that remain unsolved in the coalbed gas geochemistry include the variation mechanism, controlling factors and application of carbon and hydrogen isotopes of methane, the relation between the values of δ¹³C₁ and Ro, the systematic classification scheme and criterion of genetic types, and the application of the coalbed gas geochemistry in evaluating target districts of the coalbed gas exploration.     

Crystallography: crystallographic evidence for deviating C3b structure

Activation of the protein C3 into C3b in the complement pathway is a crucial step in the complement immune response against pathogenic, immunogenic and apoptotic particles. Ajees et al. describe a crystal structure for C3b that deviates from the one reported by Janssen et al. and by Wiesmann et al.. We have reanalysed the data deposited by Ajees et al. and have discovered features that are inconsistent with the known physical properties of macromolecular structures and their diffraction data. Our findings therefore call into question the crystal structure for C3b reported by Ajees et al..