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.     

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.     

Efficient organic carbon burial in the Bengal fan sustained by the Himalayan erosional system

Continental erosion controls atmospheric carbon dioxide levels on geological timescales through silicate weathering, riverine transport and subsequent burial of organic carbon in oceanic sediments. The efficiency of organic carbon deposition in sedimentary basins is however limited by the organic carbon load capacity of the sediments and organic carbon oxidation in continental margins. At the global scale, previous studies have suggested that about 70 per cent of riverine organic carbon is returned to the atmosphere, such as in the Amazon basin. Here we present a comprehensive organic carbon budget for the Himalayan erosional system, including source rocks, river sediments and marine sediments buried in the Bengal fan. We show that organic carbon export is controlled by sediment properties, and that oxidative loss is negligible during transport and deposition to the ocean. Our results indicate that 70 to 85 per cent of the organic carbon is recent organic matter captured during transport, which serves as a net sink for atmospheric carbon dioxide. The amount of organic carbon deposited in the Bengal basin represents about 10 to 20 per cent of the total terrestrial organic carbon buried in oceanic sediments. High erosion rates in the Himalayas generate high sedimentation rates and low oxygen availability in the Bay of Bengal that sustain the observed extreme organic carbon burial efficiency. Active orogenic systems generate enhanced physical erosion and the resulting organic carbon burial buffers atmospheric carbon dioxide levels, thereby exerting a negative feedback on climate over geological timescales.     

大洋缺氧事件的碳稳定同位素响应

从碳稳定同位素组成及其分馏机理出发 ,系统探讨了大洋缺氧事件与海相碳酸盐和有机碳稳定同位素分馏之间的关系。缺氧事件期间 ,由于生物大批死亡和快速埋藏 ,其分解消耗海水中大量的溶解氧 ,引起大洋水体缺氧 ,富含 1 2 C的有机质从而得以大量保存 ;相应地大气和海水中富 1 3 C,同期海相碳酸盐岩碳同位素 δ值 (δ1 3C)正偏。在世界各地缺氧事件层内 ,无一例外地碳酸盐岩碳稳定同位素出现了不同程度的正偏 ,Cenomanian- Turonian 界线偏幅达～2‰。海相碳酸盐与有机质碳稳定同位素变化不仅可以提供地质历史中有机碳埋藏量的记录。研究全球碳循环变化 ,还可能追溯有机碳风化和埋藏速率的变化 ,定性地恢复大气 p CO2 变化。     

Effect of evaporite deposition on Early Cretaceous carbon and sulphur cycling

The global carbon and sulphur cycles are central to our understanding of the Earth's history, because changes in the partitioning between the reduced and oxidized reservoirs of these elements are the primary control on atmospheric oxygen concentrations. In modern marine sediments, the burial rates of reduced carbon and sulphur are positively coupled, but high-resolution isotope records indicate that these rates were inversely related during the Early Cretaceous period. This inverse relationship is difficult to reconcile with our understanding of the processes that control organic matter remineralization and pyrite burial. Here we show that the inverse correlation can be explained by the deposition of evaporites during the opening of the South Atlantic Ocean basin. Evaporite deposition can alter the chemical composition of sea water, which can in turn affect the ability of sulphate-reducing bacteria to remineralize organic matter and mediate pyrite burial. We use a reaction-transport model to quantify these effects, and the resulting changes in the burial rates of carbon and sulphur, during the Early Cretaceous period. Our results indicate that deposition of the South Atlantic evaporites removed enough sulphate from the ocean temporarily to reduce biologically mediated pyrite burial and organic matter remineralization by up to fifty per cent, thus explaining the inverse relationship between the burial rates of reduced carbon and sulphur during this interval. Furthermore, our findings suggest that the effect of changing seawater sulphate concentrations on the marine subsurface biosphere may be the key to understanding other large-scale perturbations of the global carbon and sulphur cycles.     

Palaeoceanography: methane release in the Early Jurassic period

Dramatic global warming, triggered by release of methane from clathrates, has been postulated to have occurred during the early Toarcian age in the Early Jurassic period. Kemp et al. claim that this methane was released at three points, as recorded by three sharp excursions of delta13C(org) of up to 3 per thousand magnitude. But they discount another explanation for the excursions: namely that some, perhaps all, of the rapid excursions could be a local signature of a euxinic basin caused by recycling of isotopically light carbon from the lower water column. This idea has been proposed previously (see ref. 3, for example) and is supported by the lack evidence for negative delta13C excursions in coeval belemnite rostra. Kemp et al. dismiss this alternative, claiming that each abrupt shift would have required the recycling of about double the amount of organic carbon that is currently present in the modern ocean; however, their measurements are not from an ocean but from a restricted, epicontinental seaway and so would not require whole-ocean mixing to achieve the excursions.     

The evolution of the marine phosphate reservoir

Phosphorus is a biolimiting nutrient that has an important role in regulating the burial of organic matter and the redox state of the ocean-atmosphere system. The ratio of phosphorus to iron in iron-oxide-rich sedimentary rocks can be used to track dissolved phosphate concentrations if the dissolved silica concentration of sea water is estimated. Here we present iron and phosphorus concentration ratios from distal hydrothermal sediments and iron formations through time to study the evolution of the marine phosphate reservoir. The data suggest that phosphate concentrations have been relatively constant over the Phanerozoic eon, the past 542 million years (Myr) of Earth's history. In contrast, phosphate concentrations seem to have been elevated in Precambrian oceans. Specifically, there is a peak in phosphorus-to-iron ratios in Neoproterozoic iron formations dating from ～750 to ～635?Myr ago, indicating unusually high dissolved phosphate concentrations in the aftermath of widespread, low-latitude 'snowball Earth' glaciations. An enhanced postglacial phosphate flux would have caused high rates of primary productivity and organic carbon burial and a transition to more oxidizing conditions in the ocean and atmosphere. The snowball Earth glaciations and Neoproterozoic oxidation are both suggested as triggers for the evolution and radiation of metazoans. We propose that these two factors are intimately linked; a glacially induced nutrient surplus could have led to an increase in atmospheric oxygen, paving the way for the rise of metazoan life.     

Release of methane from a volcanic basin as a mechanism for initial Eocene global warming

A 200,000-yr interval of extreme global warming marked the start of the Eocene epoch about 55 million years ago. Negative carbon- and oxygen-isotope excursions in marine and terrestrial sediments show that this event was linked to a massive and rapid (approximately 10,000 yr) input of isotopically depleted carbon. It has been suggested previously that extensive melting of gas hydrates buried in marine sediments may represent the carbon source and has caused the global climate change. Large-scale hydrate melting, however, requires a hitherto unknown triggering mechanism. Here we present evidence for the presence of thousands of hydrothermal vent complexes identified on seismic reflection profiles from the V?ring and M?re basins in the Norwegian Sea. We propose that intrusion of voluminous mantle-derived melts in carbon-rich sedimentary strata in the northeast Atlantic may have caused an explosive release of methane--transported to the ocean or atmosphere through the vent complexes--close to the Palaeocene/Eocene boundary. Similar volcanic and metamorphic processes may explain climate events associated with other large igneous provinces such as the Siberian Traps (approximately 250 million years ago) and the Karoo Igneous Province (approximately 183 million years ago).     

The long-term carbon cycle, fossil fuels and atmospheric composition

The long-term carbon cycle operates over millions of years and involves the exchange of carbon between rocks and the Earth's surface. There are many complex feedback pathways between carbon burial, nutrient cycling, atmospheric carbon dioxide and oxygen, and climate. New calculations of carbon fluxes during the Phanerozoic eon (the past 550 million years) illustrate how the long-term carbon cycle has affected the burial of organic matter and fossil-fuel formation, as well as the evolution of atmospheric composition.     

Climate-driven trends in contemporary ocean productivity

Contributing roughly half of the biosphere's net primary production (NPP), photosynthesis by oceanic phytoplankton is a vital link in the cycling of carbon between living and inorganic stocks. Each day, more than a hundred million tons of carbon in the form of CO2 are fixed into organic material by these ubiquitous, microscopic plants of the upper ocean, and each day a similar amount of organic carbon is transferred into marine ecosystems by sinking and grazing. The distribution of phytoplankton biomass and NPP is defined by the availability of light and nutrients (nitrogen, phosphate, iron). These growth-limiting factors are in turn regulated by physical processes of ocean circulation, mixed-layer dynamics, upwelling, atmospheric dust deposition, and the solar cycle. Satellite measurements of ocean colour provide a means of quantifying ocean productivity on a global scale and linking its variability to environmental factors. Here we describe global ocean NPP changes detected from space over the past decade. The period is dominated by an initial increase in NPP of 1,930 teragrams of carbon a year (Tg C yr(-1)), followed by a prolonged decrease averaging 190 Tg C yr(-1). These trends are driven by changes occurring in the expansive stratified low-latitude oceans and are tightly coupled to coincident climate variability. This link between the physical environment and ocean biology functions through changes in upper-ocean temperature and stratification, which influence the availability of nutrients for phytoplankton growth. The observed reductions in ocean productivity during the recent post-1999 warming period provide insight on how future climate change can alter marine food webs.     

Geochemical evidence for widespread euxinia in the later Cambrian ocean

Widespread anoxia in the ocean is frequently invoked as a primary driver of mass extinction as well as a long-term inhibitor of evolutionary radiation on early Earth. In recent biogeochemical studies it has been hypothesized that oxygen deficiency was widespread in subsurface water masses of later Cambrian oceans, possibly influencing evolutionary events during this time. Physical evidence of widespread anoxia in Cambrian oceans has remained elusive and thus its potential relationship to the palaeontological record remains largely unexplored. Here we present sulphur isotope records from six globally distributed stratigraphic sections of later Cambrian marine rocks (about 499 million years old). We find a positive sulphur isotope excursion in phase with the Steptoean Positive Carbon Isotope Excursion (SPICE), a large and rapid excursion in the marine carbon isotope record, which is thought to be indicative of a global carbon cycle perturbation. Numerical box modelling of the paired carbon sulphur isotope data indicates that these isotope shifts reflect transient increases in the burial of organic carbon and pyrite sulphur in sediments deposited under large-scale anoxic and sulphidic (euxinic) conditions. Independently, molybdenum abundances in a coeval black shale point convincingly to the transient spread of anoxia. These results identify the SPICE interval as the best characterized ocean anoxic event in the pre-Mesozoic ocean and an extreme example of oxygen deficiency in the later Cambrian ocean. Thus, a redox structure similar to those in Proterozoic oceans may have persisted or returned in the oceans of the early Phanerozoic eon. Indeed, the environmental challenges presented by widespread anoxia may have been a prevalent if not dominant influence on animal evolution in Cambrian oceans.     

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.     

贵州拉也剖面下Kellwasser事件生物地层及化学地层特征研究

为研究下Kellwasser事件的生物地层及化学地层特征, 对贵州拉也剖面进行细致的牙形石生物地层学和高分辨率化学地层学研究。结果表明, 剖面底部无机碳同位素及有机碳同位素有显著正向偏移, 样品LY-8代表的层位为下Kellwasser事件的界线。Kellwasser事件碳同位素变化的主要原因是有机碳埋藏量的增加, 可能是由初级生产力增加和缺氧环境共同造成的。     

Cretaceous oceanic anoxic event 2 triggered by a massive magmatic episode

Oceanic anoxic events (OAEs) were episodes of widespread marine anoxia during which large amounts of organic carbon were buried on the ocean floor under oxygen-deficient bottom waters. OAE2, occurring at the Cenomanian/Turonian boundary (about 93.5 Myr ago), is the most widespread and best defined OAE of the mid-Cretaceous. Although the enhanced burial of organic matter can be explained either through increased primary productivity or enhanced preservation scenarios, the actual trigger mechanism, corresponding closely to the onset of these episodes of increased carbon sequestration, has not been clearly identified. It has been postulated that large-scale magmatic activity initially triggered OAE2 (refs 4, 5), but a direct proxy of magmatism preserved in the sedimentary record coinciding closely with the onset of OAE2 has not yet been found. Here we report seawater osmium isotope ratios in organic-rich sediments from two distant sites. We find that at both study sites the marine osmium isotope record changes abruptly just at or before the onset of OAE2. Using a simple two-component mixing equation, we calculate that over 97 per cent of the total osmium content in contemporaneous seawater at both sites is magmatic in origin, a approximately 30-50-fold increase relative to pre-OAE conditions. Furthermore, the magmatic osmium isotope signal appears slightly before the OAE2-as indicated by carbon isotope ratios-suggesting a time-lag of up to approximately 23 kyr between magmatism and the onset of significant organic carbon burial, which may reflect the reaction time of the global ocean system. Our marine osmium isotope data are indicative of a widespread magmatic pulse at the onset of OAE2, which may have triggered the subsequent deposition of large amounts of organic matter.     

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 …     

Variations of sulfur and carbon isotopes in seawater during the Doushantuo stage in late Neoproterozoic

The Doushantuo Formation of the Sinian System in the Yangtze area is the first sedimentary stratigraphic unit after the Neoproterozoic Snowball Earth event[1], named the Nantuo Glaciation in south China. There are not only phosphorite and manganese mineralized beds[2], but also a series of biome which represents the biological radiation in Neoproterozoic[3] found in this formation. It is important to study the palaeoenvironment and the early biological evolution implied in the Doushantuo …     

Preservation of organic matter in sediments promoted by iron

The biogeochemical cycles of iron and organic carbon are strongly interlinked. In oceanic waters, organic ligands have been shown to control the concentration of dissolved iron. In soils, solid iron phases shelter and preserve organic carbon, but the role of iron in the preservation of organic matter in sediments has not been clearly established. Here we use an iron reduction method previously applied to soils to determine the amount of organic carbon associated with reactive iron phases in sediments of various mineralogies collected from a wide range of depositional environments. Our findings suggest that 21.5?±?8.6 per cent of the organic carbon in sediments is directly bound to reactive iron phases. We further estimate that a global mass of (19-45)?×?10(15)?grams of organic carbon is preserved in surface marine sediments as a result of its association with iron. We propose that these associations between organic carbon and iron, which are formed primarily through co-precipitation and/or direct chelation, promote the preservation of organic carbon in sediments. Because reactive iron phases are metastable over geological timescales, we suggest that they serve as an efficient 'rusty sink' for organic carbon, acting as a key factor in the long-term storage of organic carbon and thus contributing to the global cycles of carbon, oxygen and sulphur.     

Reburial of fossil organic carbon in marine sediments

Marine sediments act as the ultimate sink for organic carbon, sequestering otherwise rapidly cycling carbon for geologic timescales. Sedimentary organic carbon burial appears to be controlled by oxygen exposure time in situ, and much research has focused on understanding the mechanisms of preservation of organic carbon. In this context, combustion-derived black carbon has received attention as a form of refractory organic carbon that may be preferentially preserved in soils and sediments. However, little is understood about the environmental roles, transport and distribution of black carbon. Here we apply isotopic analyses to graphitic black carbon samples isolated from pre-industrial marine and terrestrial sediments. We find that this material is terrestrially derived and almost entirely depleted of radiocarbon, suggesting that it is graphite weathered from rocks, rather than a combustion product. The widespread presence of fossil graphitic black carbon in sediments has therefore probably led to significant overestimates of burial of combustion-derived black carbon in marine sediments. It could be responsible for biasing radiocarbon dating of sedimentary organic carbon, and also reveals a closed loop in the carbon cycle. Depending on its susceptibility to oxidation, this recycled carbon may be locked away from the biologically mediated carbon cycle for many geologic cycles.     

Secular variation in carbon isotope ratios from Upper Proterozoic successions of Svalbard and East Greenland

Analyses of stratigraphically continuous suites of samples from Upper Proterozoic sedimentary successions of East Greenland, Spitsbergen and Nordaustlandet (Svalbard) provide an approximation to the secular variation in carbon isotope ratios during a geologically and biologically important period of change from around 900 million years ago to the beginning of the Cambrian period. Late Riphean carbonates and organic material show a stratigraphically useful pattern of enrichment in 13C relative to Phanerozoic or earlier Proterozoic samples. Isotopic compositions of isolated samples from other localities are consistent with a worldwide extended interval of enhanced organic burial and consequent net survival of oxidized material, probably O2, just before the initial radiation of metazoans.     

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.