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.     

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.     

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。     

Massive dissociation of gas hydrate during a Jurassic oceanic anoxic event

In the Jurassic period, the Early Toarcian oceanic anoxic event (about 183 million years ago) is associated with exceptionally high rates of organic-carbon burial, high palaeotemperatures and significant mass extinction. Heavy carbon-isotope compositions in rocks and fossils of this age have been linked to the global burial of organic carbon, which is isotopically light. In contrast, examples of light carbon-isotope values from marine organic matter of Early Toarcian age have been explained principally in terms of localized upwelling of bottom water enriched in 12C versus 13C (refs 1,2,5,6). Here, however, we report carbon-isotope analyses of fossil wood which demonstrate that isotopically light carbon dominated all the upper oceanic, biospheric and atmospheric carbon reservoirs, and that this occurred despite the enhanced burial of organic carbon. We propose that--as has been suggested for the Late Palaeocene thermal maximum, some 55 million years ago--the observed patterns were produced by voluminous and extremely rapid release of methane from gas hydrate contained in marine continental-margin sediments.     

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.     

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.     

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.     

Atmospheric carbon dioxide concentrations over the past 60 million years

Knowledge of the evolution of atmospheric carbon dioxide concentrations throughout the Earth's history is important for a reconstruction of the links between climate and radiative forcing of the Earth's surface temperatures. Although atmospheric carbon dioxide concentrations in the early Cenozoic era (about 60 Myr ago) are widely believed to have been higher than at present, there is disagreement regarding the exact carbon dioxide levels, the timing of the decline and the mechanisms that are most important for the control of CO2 concentrations over geological timescales. Here we use the boron-isotope ratios of ancient planktonic foraminifer shells to estimate the pH of surface-layer sea water throughout the past 60 million years, which can be used to reconstruct atmospheric CO2 concentrations. We estimate CO2 concentrations of more than 2,000 p.p.m. for the late Palaeocene and earliest Eocene periods (from about 60 to 52 Myr ago), and find an erratic decline between 55 and 40 Myr ago that may have been caused by reduced CO2 outgassing from ocean ridges, volcanoes and metamorphic belts and increased carbon burial. Since the early Miocene (about 24 Myr ago), atmospheric CO2 concentrations appear to have remained below 500 p.p.m. and were more stable than before, although transient intervals of CO2 reduction may have occurred during periods of rapid cooling approximately 15 and 3 Myr ago.     

Old-growth forests as global carbon sinks

Old-growth forests remove carbon dioxide from the atmosphere at rates that vary with climate and nitrogen deposition. The sequestered carbon dioxide is stored in live woody tissues and slowly decomposing organic matter in litter and soil. Old-growth forests therefore serve as a global carbon dioxide sink, but they are not protected by international treaties, because it is generally thought that ageing forests cease to accumulate carbon. Here we report a search of literature and databases for forest carbon-flux estimates. We find that in forests between 15 and 800 years of age, net ecosystem productivity (the net carbon balance of the forest including soils) is usually positive. Our results demonstrate that old-growth forests can continue to accumulate carbon, contrary to the long-standing view that they are carbon neutral. Over 30 per cent of the global forest area is unmanaged primary forest, and this area contains the remaining old-growth forests. Half of the primary forests (6 x 10(8) hectares) are located in the boreal and temperate regions of the Northern Hemisphere. On the basis of our analysis, these forests alone sequester about 1.3 +/- 0.5 gigatonnes of carbon per year. Thus, our findings suggest that 15 per cent of the global forest area, which is currently not considered when offsetting increasing atmospheric carbon dioxide concentrations, provides at least 10 per cent of the global net ecosystem productivity. Old-growth forests accumulate carbon for centuries and contain large quantities of it. We expect, however, that much of this carbon, even soil carbon, will move back to the atmosphere if these forests are disturbed.     

Variable ageing and storage of dissolved organic components in the open ocean

Seawater dissolved organic matter (DOM) is the largest reservoir of exchangeable organic carbon in the ocean, comparable in quantity to atmospheric carbon dioxide. The composition, turnover times and fate of all but a few planktonic constituents of this material are, however, largely unknown. Models of ocean carbon cycling are thus limited by the need for information on temporal scales of carbon storage in DOM subcomponents, produced via the 'biological pump', relative to their recycling by bacteria. Here we show that carbohydrate- and protein-like substances in the open Atlantic and Pacific oceans, though often significantly aged, comprise younger fractions of the DOM, whereas dissolved lipophilic material exhibits up to approximately 90 per cent fossil character. In contrast to the millennial mean ages of DOM observed throughout the water column, weighted mean turnover times of DOM in the surface ocean are only decadal in magnitude. An observed size-age continuum further demonstrates that small dissolved molecules are the most highly aged forms of organic matter, cycling much more slowly than larger, younger dissolved and particulate precursors, and directly links oceanic organic matter age and size with reactivity.     

Weak response of the Atlantic thermohaline circulation to an increase of atmospheric carbon dioxide in IAP／LASG Climate System Model

Response of the Atlantic thermohaline circulation (THC) to global warming is examined by using the climate system model developed at IAP/LASG. The evidence indicates that the gradually warming climate associated with the increased atmospheric carbon dioxide leads to a warmer and fresher sea surface water at the high latitudes of the North Atlantic Ocean, which prevents the down-welling of the surface water. The succedent reduction of the pole-toequator meridional potential density gradient finally results in the decrease of the THC in intensity. When the atmospheric carbon dioxide is doubled, the maximum value of the Atlantic THC decreases approximately by 8%. The associated poleward oceanic heat transport also becomes weaker. This kind of THC weakening centralizes mainly in the northern part of the North Atlantic basin, indicating briefly a local scale adjustment rather than a loop oscillation with the whole Atlantic “conveyor belt” decelerating.     

A Cenozoic record of the equatorial Pacific carbonate compensation depth

Atmospheric carbon dioxide concentrations and climate are regulated on geological timescales by the balance between carbon input from volcanic and metamorphic outgassing and its removal by weathering feedbacks; these feedbacks involve the erosion of silicate rocks and organic-carbon-bearing rocks. The integrated effect of these processes is reflected in the calcium carbonate compensation depth, which is the oceanic depth at which calcium carbonate is dissolved. Here we present a carbonate accumulation record that covers the past 53 million years from a depth transect in the equatorial Pacific Ocean. The carbonate compensation depth tracks long-term ocean cooling, deepening from 3.0-3.5?kilometres during the early Cenozoic (approximately 55?million years ago) to 4.6 kilometres at present, consistent with an overall Cenozoic increase in weathering. We find large superimposed fluctuations in carbonate compensation depth during the middle and late Eocene. Using Earth system models, we identify changes in weathering and the mode of organic-carbon delivery as two key processes to explain these large-scale Eocene fluctuations of the carbonate compensation depth.     

Climate sensitivity constrained by CO2 concentrations over the past 420 million years

A firm understanding of the relationship between atmospheric carbon dioxide concentration and temperature is critical for interpreting past climate change and for predicting future climate change. A recent synthesis suggests that the increase in global-mean surface temperature in response to a doubling of the atmospheric carbon dioxide concentration, termed 'climate sensitivity', is between 1.5 and 6.2 degrees C (5-95 per cent likelihood range), but some evidence is inconsistent with this range. Moreover, most estimates of climate sensitivity are based on records of climate change over the past few decades to thousands of years, when carbon dioxide concentrations and global temperatures were similar to or lower than today, so such calculations tend to underestimate the magnitude of large climate-change events and may not be applicable to climate change under warmer conditions in the future. Here we estimate long-term equilibrium climate sensitivity by modelling carbon dioxide concentrations over the past 420 million years and comparing our calculations with a proxy record. Our estimates are broadly consistent with estimates based on short-term climate records, and indicate that a weak radiative forcing by carbon dioxide is highly unlikely on multi-million-year timescales. We conclude that a climate sensitivity greater than 1.5 degrees C has probably been a robust feature of the Earth's climate system over the past 420 million years, regardless of temporal scaling.     

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 changes to the atmospheric CO2 sink in the subtropical North Pacific Ocean

The oceans represent a significant sink for atmospheric carbon dioxide. Variability in the strength of this sink occurs on interannual timescales, as a result of regional and basin-scale changes in the physical and biological parameters that control the flux of this greenhouse gas into and out of the surface mixed layer. Here we analyse a 13-year time series of oceanic carbon dioxide measurements from station ALOHA in the subtropical North Pacific Ocean near Hawaii, and find a significant decrease in the strength of the carbon dioxide sink over the period 1989-2001. We show that much of this reduction in sink strength can be attributed to an increase in the partial pressure of surface ocean carbon dioxide caused by excess evaporation and the accompanying concentration of solutes in the water mass. Our results suggest that carbon dioxide uptake by ocean waters can be strongly influenced by changes in regional precipitation and evaporation patterns brought on by climate variability.     

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.     

Negligible glacial-interglacial variation in continental chemical weathering rates

Chemical weathering of the continents is central to the regulation of atmospheric carbon dioxide concentrations, and hence global climate. On million-year timescales silicate weathering leads to the draw-down of carbon dioxide, and on millennial timescales chemical weathering affects the calcium carbonate saturation state of the oceans and hence their uptake of carbon dioxide. However, variations in chemical weathering rates over glacial-interglacial cycles remain uncertain. During glacial periods, cold and dry conditions reduce the rate of chemical weathering, but intense physical weathering and the exposure of carbonates on continental shelves due to low sea levels may increase this rate. Here we present high-resolution records of the lead isotope composition of ferromanganese crusts from the North Atlantic Ocean that cover the past 550,000 years. Combining these records with a simple quantitative model of changes in the lead isotope composition of the deep North Atlantic Ocean in response to chemical weathering, we find that chemical weathering rates were two to three times lower in the glaciated interior of the North Atlantic Region during glacial periods than during the intervening interglacial periods. This decrease roughly balances the increase in chemical weathering caused by the exposure of continental shelves, indicating that chemical weathering rates remained relatively constant on glacial-interglacial timescales. On timescales of more than a million years, however, we suggest that enhanced weathering of silicate glacial sediments during interglacial periods results in a net draw-down of atmospheric carbon dioxide, creating a positive feedback on global climate that, once initiated, promotes cooling and further glaciation.     

Evidence for decoupling of atmospheric CO2 and global climate during the Phanerozoic eon

Atmospheric carbon dioxide concentrations are believed to drive climate changes from glacial to interglacial modes, although geological and astronomical mechanisms have been invoked as ultimate causes. Additionally, it is unclear whether the changes between cold and warm modes should be regarded as a global phenomenon, affecting tropical and high-latitude temperatures alike, or if they are better described as an expansion and contraction of the latitudinal climate zones, keeping equatorial temperatures approximately constant. Here we present a reconstruction of tropical sea surface temperatures throughout the Phanerozoic eon (the past approximately 550 Myr) from our database of oxygen isotopes in calcite and aragonite shells. The data indicate large oscillations of tropical sea surface temperatures in phase with the cold-warm cycles, thus favouring the idea of climate variability as a global phenomenon. But our data conflict with a temperature reconstruction using an energy balance model that is forced by reconstructed atmospheric carbon dioxide concentrations. The results can be reconciled if atmospheric carbon dioxide concentrations were not the principal driver of climate variability on geological timescales for at least one-third of the Phanerozoic eon, or if the reconstructed carbon dioxide concentrations are not reliable.     

Palaeoclimatology: the record for marine isotopic stage 11

The marine isotopic stage 11 (MIS 11) is an extraordinarily long interglacial period in the Earth's history that occurred some 400,000 years ago and lasted for about 30,000 years. During this period there were weak, astronomically induced changes in the distribution of solar energy reaching the Earth. The conditions of this orbital climate forcing are similar to those of today's interglacial period, and they rendered the climate susceptible to other forcing--for example, to changes in the level of atmospheric carbon dioxide. Here we use ice-core data from the Antarctic Vostok core to reconstruct a complete atmospheric carbon dioxide record for MIS 11. The record indicates that values for carbon dioxide throughout the interglacial period were close to the Earth's pre-industrial levels and that both solar energy and carbon dioxide may have helped to make MIS 11 exceptionally long. Anomalies in the oceanic carbonate system recorded in marine sediments at the time, for example while coral reefs were forming, apparently left no signature on atmospheric carbon dioxide concentrations.     

Activation of old carbon by erosion of coastal and subsea permafrost in Arctic Siberia

The future trajectory of greenhouse gas concentrations depends on interactions between climate and the biogeosphere. Thawing of Arctic permafrost could release significant amounts of carbon into the atmosphere in this century. Ancient Ice Complex deposits outcropping along the ~7,000-kilometre-long coastline of the East Siberian Arctic Shelf (ESAS), and associated shallow subsea permafrost, are two large pools of permafrost carbon, yet their vulnerabilities towards thawing and decomposition are largely unknown. Recent Arctic warming is stronger than has been predicted by several degrees, and is particularly pronounced over the coastal ESAS region. There is thus a pressing need to improve our understanding of the links between permafrost carbon and climate in this relatively inaccessible region. Here we show that extensive release of carbon from these Ice Complex deposits dominates (57?±?2 per cent) the sedimentary carbon budget of the ESAS, the world’s largest continental shelf, overwhelming the marine and topsoil terrestrial components. Inverse modelling of the dual-carbon isotope composition of organic carbon accumulating in ESAS surface sediments, using Monte Carlo simulations to account for uncertainties, suggests that 44?±?10 teragrams of old carbon is activated annually from Ice Complex permafrost, an order of magnitude more than has been suggested by previous studies. We estimate that about two-thirds (66?±?16 per cent) of this old carbon escapes to the atmosphere as carbon dioxide, with the remainder being re-buried in shelf sediments. Thermal collapse and erosion of these carbon-rich Pleistocene coastline and seafloor deposits may accelerate with Arctic amplification of climate warming.