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.     

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.     

The Southern Ocean biogeochemical divide

Modelling studies have demonstrated that the nutrient and carbon cycles in the Southern Ocean play a central role in setting the air-sea balance of CO(2) and global biological production. Box model studies first pointed out that an increase in nutrient utilization in the high latitudes results in a strong decrease in the atmospheric carbon dioxide partial pressure (pCO2). This early research led to two important ideas: high latitude regions are more important in determining atmospheric pCO2 than low latitudes, despite their much smaller area, and nutrient utilization and atmospheric pCO2 are tightly linked. Subsequent general circulation model simulations show that the Southern Ocean is the most important high latitude region in controlling pre-industrial atmospheric CO(2) because it serves as a lid to a larger volume of the deep ocean. Other studies point out the crucial role of the Southern Ocean in the uptake and storage of anthropogenic carbon dioxide and in controlling global biological production. Here we probe the system to determine whether certain regions of the Southern Ocean are more critical than others for air-sea CO(2) balance and the biological export production, by increasing surface nutrient drawdown in an ocean general circulation model. We demonstrate that atmospheric CO(2) and global biological export production are controlled by different regions of the Southern Ocean. The air-sea balance of carbon dioxide is controlled mainly by the biological pump and circulation in the Antarctic deep-water formation region, whereas global export production is controlled mainly by the biological pump and circulation in the Subantarctic intermediate and mode water formation region. The existence of this biogeochemical divide separating the Antarctic from the Subantarctic suggests that it may be possible for climate change or human intervention to modify one of these without greatly altering the other.     

Reduced calcification of marine plankton in response to increased atmospheric CO2

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments. This is important in regulating marine carbon cycling and ocean-atmosphere CO2 exchange. The present rise in atmospheric CO2 levels causes significant changes in surface ocean pH and carbonate chemistry. Such changes have been shown to slow down calcification in corals and coralline macroalgae, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica. This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.     

High temperatures in the Late Cretaceous Arctic Ocean

To understand the climate dynamics of the warm, equable greenhouse world of the Late Cretaceous period, it is important to determine polar palaeotemperatures. The early palaeoceanographic history of the Arctic Ocean has, however, remained largely unknown, because the sea floor and underlying deposits are usually inaccessible beneath a cover of floating ice. A shallow piston core taken from a drifting ice island in 1970 fortuitously retrieved unconsolidated Upper Cretaceous organic-rich sediment from Alpha ridge, a submarine elevated feature of probable oceanic origin. A lack of carbonate in the sediments from this core has prevented the use of traditional oxygen-isotope palaeothermometry. Here we determine Arctic palaeotemperatures from these Upper Cretaceous deposits using TEX86, a new palaeothermometer that is based on the composition of membrane lipids derived from a ubiquitous component of marine plankton, Crenarchaeota. From these analyses we infer an average sea surface temperature of approximately 15 degrees C for the Arctic Ocean about 70 million years ago. This calibration point implies an Equator-to-pole gradient in sea surface temperatures of approximately 15 degrees C during this interval and, by extrapolation, we suggest that polar waters were generally warmer than 20 degrees C during the middle Cretaceous (approximately 90 million years ago).     

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。     

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.     

The influence of Antarctic sea ice on glacial-interglacial CO2 variations

Ice-core measurements indicate that atmospheric CO2 concentrations during glacial periods were consistently about 80 parts per million lower than during interglacial periods. Previous explanations for this observation have typically had difficulty accounting for either the estimated glacial O2 concentrations in the deep sea, 13C/12C ratios in Antarctic surface waters, or the depth of calcite saturation; also lacking is an explanation for the strong link between atmospheric CO2 and Antarctic air temperature. There is growing evidence that the amount of deep water upwelling at low latitudes is significantly overestimated in most ocean general circulation models and simpler box models previously used to investigate this problem. Here we use a box model with deep-water upwelling confined to south of 55 degrees S to investigate the glacial-interglacial linkages between Antarctic air temperature and atmospheric CO2 variations. We suggest that low glacial atmospheric CO2 levels might result from reduced deep-water ventilation associated with either year-round Antarctic sea-ice coverage, or wintertime coverage combined with ice-induced stratification during the summer. The model presented here reproduces 67 parts per million of the observed glacial-interglacial CO2 difference, as a result of reduced air-sea gas exchange in the Antarctic region, and is generally consistent with the additional observational constraints.     

A carbon isotope challenge to the snowball Earth

The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation. High partial pressures of atmospheric CO(2) (pCO2; from 20,000 to 90,000?p.p.m.v.) in the aftermath of the Marinoan glaciation (～635?Myr ago) have been inferred from both boron and triple oxygen isotopes. These pCO2 values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise. The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units, provide estimates lower than 3,200?p.p.m.v.--and possibly as low as the current value of ～400?p.p.m.v. Our new constraint, and our re-interpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.     

Snowball Earth termination by destabilization of equatorial permafrost methane clathrate

The start of the Ediacaran period is defined by one of the most severe climate change events recorded in Earth history--the recovery from the Marinoan 'snowball' ice age, approximately 635 Myr ago (ref. 1). Marinoan glacial-marine deposits occur at equatorial palaeolatitudes, and are sharply overlain by a thin interval of carbonate that preserves marine carbon and sulphur isotopic excursions of about -5 and +15 parts per thousand, respectively; these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise. This abrupt transition records a climate system in profound disequilibrium and contrasts sharply with the cyclical stratigraphic signal imparted by the balanced feedbacks modulating Phanerozoic deglaciation. Hypotheses accounting for the abruptness of deglaciation include ice albedo feedback, deep-ocean out-gassing during post-glacial oceanic overturn or methane hydrate destabilization. Here we report the broadest range of oxygen isotope values yet measured in marine sediments (-25 per thousand to +12 per thousand) in methane seeps in Marinoan deglacial sediments underlying the cap carbonate. This range of values is likely to be the result of mixing between ice-sheet-derived meteoric waters and clathrate-derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater. The equatorial palaeolatitude implies a highly volatile shelf permafrost pool that is an order of magnitude larger than that of the present day. A pool of this size could have provided a massive biogeochemical feedback capable of triggering deglaciation and accounting for the global postglacial marine carbon and sulphur isotopic excursions, abrupt unidirectional warming, cap carbonate deposition, and a marine oxygen crisis. Our findings suggest that methane released from low-latitude permafrost clathrates therefore acted as a trigger and/or strong positive feedback for deglaciation and warming. Methane hydrate destabilization is increasingly suspected as an important positive feedback to climate change that coincides with critical boundaries in the geological record and may represent one particularly important mechanism active during conditions of strong climate forcing.     

Holocene Southern Ocean surface temperature variability west of the Antarctic Peninsula

The disintegration of ice shelves, reduced sea-ice and glacier extent, and shifting ecological zones observed around Antarctica highlight the impact of recent atmospheric and oceanic warming on the cryosphere. Observations and models suggest that oceanic and atmospheric temperature variations at Antarctica's margins affect global cryosphere stability, ocean circulation, sea levels and carbon cycling. In particular, recent climate changes on the Antarctic Peninsula have been dramatic, yet the Holocene climate variability of this region is largely unknown, limiting our ability to evaluate ongoing changes within the context of historical variability and underlying forcing mechanisms. Here we show that surface ocean temperatures at the continental margin of the western Antarctic Peninsula cooled by 3-4 °C over the past 12,000 years, tracking the Holocene decline of local (65° S) spring insolation. Our results, based on TEX(86) sea surface temperature (SST) proxy evidence from a marine sediment core, indicate the importance of regional summer duration as a driver of Antarctic seasonal sea-ice fluctuations. On millennial timescales, abrupt SST fluctuations of 2-4 °C coincide with globally recognized climate variability. Similarities between our SSTs, Southern Hemisphere westerly wind reconstructions and El Ni?o/Southern Oscillation variability indicate that present climate teleconnections between the tropical Pacific Ocean and the western Antarctic Peninsula strengthened late in the Holocene epoch. We conclude that during the Holocene, Southern Ocean temperatures at the western Antarctic Peninsula margin were tied to changes in the position of the westerlies, which have a critical role in global carbon cycling.     

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.     

Slowdown of the meridional overturning circulation in the upper Pacific Ocean

Decadal temperature fluctuations in the Pacific Ocean have a significant effect on marine ecosystems and the climate of North America. The physical mechanisms responsible for these fluctuations are poorly understood. Some theories ascribe a central role to the wind-driven meridional overturning circulation between the tropical and subtropical oceans. Here we show, from observations over the past 50 years, that this overturning circulation has been slowing down since the 1970s, causing a decrease in upwelling of about 25% in an equatorial strip between 9 degrees N and 9 degrees S. This reduction in equatorial upwelling of relatively cool water, from 47 x 10(6) to 35 x 10(6) m3 s(-1), is associated with a rise in equatorial sea surface temperatures of about 0.8 degrees C. Another effect of the slowing circulation is a reduction in the outgassing of CO2 from the equatorial Pacific Ocean-at present the largest oceanic source of carbon dioxide to the atmosphere.     

The effect of millennial-scale changes in Arabian Sea denitrification on atmospheric CO2.

Most global biogeochemical processes are known to respond to climate change, some of which have the capacity to produce feedbacks through the regulation of atmospheric greenhouse gases. Marine denitrification-the reduction of nitrate to gaseous nitrogen-is an important process in this regard, affecting greenhouse gas concentrations directly through the incidental production of nitrous oxide, and indirectly through modification of the marine nitrogen inventory and hence the biological pump for CO2. Although denitrification has been shown to vary with glacial-interglacial cycles, its response to more rapid climate change has not yet been well characterized. Here we present nitrogen isotope ratio, nitrogen content and chlorin abundance data from sediment cores with high accumulation rates on the Oman continental margin that reveal substantial millennial-scale variability in Arabian Sea denitrification and productivity during the last glacial period. The detailed correspondence of these changes with Dansgaard-Oeschger events recorded in Greenland ice cores indicates rapid, century-scale reorganization of the Arabian Sea ecosystem in response to climate excursions, mediated through the intensity of summer monsoonal upwelling. Considering the several-thousand-year residence time of fixed nitrogen in the ocean, the response of global marine productivity to changes in denitrification would have occurred at lower frequency and appears to be related to climatic and atmospheric CO2 oscillations observed in Antarctic ice cores between 20 and 60 kyr ago.     

High-resolution carbon dioxide concentration record 650,000-800,000 years before present

Changes in past atmospheric carbon dioxide concentrations can be determined by measuring the composition of air trapped in ice cores from Antarctica. So far, the Antarctic Vostok and EPICA Dome C ice cores have provided a composite record of atmospheric carbon dioxide levels over the past 650,000 years. Here we present results of the lowest 200 m of the Dome C ice core, extending the record of atmospheric carbon dioxide concentration by two complete glacial cycles to 800,000 yr before present. From previously published data and the present work, we find that atmospheric carbon dioxide is strongly correlated with Antarctic temperature throughout eight glacial cycles but with significantly lower concentrations between 650,000 and 750,000 yr before present. Carbon dioxide levels are below 180 parts per million by volume (p.p.m.v.) for a period of 3,000 yr during Marine Isotope Stage 16, possibly reflecting more pronounced oceanic carbon storage. We report the lowest carbon dioxide concentration measured in an ice core, which extends the pre-industrial range of carbon dioxide concentrations during the late Quaternary by about 10 p.p.m.v. to 172-300 p.p.m.v.     

Carbon and sulfur isotopic compositions of basal Datangpo Formation, northeastern Guizhou, South China: implications for depositional environment

Isotopic compositions of Mn-carbonate and organic carbon from the same individual samples and sulfur isotopic compositions of pyrites in the basal Datangpo Formation were analyzed. Highly 34S-enriched pyrites （834Spyrite =31.7-59.4‰） were precipitated in rel- atively occlusive pore water under anoxic condition in sediments, which is consistent with the observation of large and scattered pyrite framboids. The sulfidic deep ocean was not ＂oxidized＂ in the early Datangpo interglacial interval, thus the level of seawater sulfate remained low and marine δ34Ssulphate remained high. Low δ13Ccar （average -7.4‰） and abnormal relationship between δ13Ccar and fractionation （ΔCar-ors） imply that the negative δ13CCar excursion may have resulted from oxidation of part of a large organic carbon reservoir. High Δcar-org （average 25.1‰） implicates high CO2 level in the atmosphere. Small standard deviation （1.0‰） of δ13CCar values indicates the Mn-carbonate was precipitated near the water-sediment interface under dysoxic conditions rather than in occlusive pore water in sediments.     

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.     

Plant biomarkers in aerosols record isotopic discrimination of terrestrial photosynthesis

Carbon uptake by the oceans and by the terrestrial biosphere can be partitioned using changes in the (12)C/(13)C isotopic ratio (delta(13)C) of atmospheric carbon dioxide, because terrestrial photosynthesis strongly discriminates against (13)CO(2), whereas ocean uptake does not. This approach depends on accurate estimates of the carbon isotopic discrimination of terrestrial photosynthesis (Delta; ref. 5) at large regional scales, yet terrestrial ecosystem heterogeneity makes such estimates problematic. Here we show that ablated plant wax compounds in continental air masses can be used to estimate Delta over large spatial scales and at less than monthly temporal resolution. We measured plant waxes in continental air masses advected to Bermuda, which are mainly of North American origin, and used the wax isotopic composition to estimate Delta simply. Our estimates indicate a large (5 6 per thousand) seasonal variation in Delta of the temperate North American biosphere, with maximum discrimination occurring in late spring, coincident with the onset of production. We suggest that the observed seasonality arises from several factors, including seasonal shifts in the proportions of production by C(3) and C(4) plants, and environmentally controlled adjustments in the photosynthetic discrimination of C(3)-plant-dominated ecosystems.     

Late Miocene decoupling of oceanic warmth and atmospheric carbon dioxide forcing

Deep-time palaeoclimate studies are vitally important for developing a complete understanding of climate responses to changes in the atmospheric carbon dioxide concentration (that is, the atmospheric partial pressure of CO(2), p(co(2))). Although past studies have explored these responses during portions of the Cenozoic era (the most recent 65.5 million years (Myr) of Earth history), comparatively little is known about the climate of the late Miocene (～12-5 Myr ago), an interval with p(co(2)) values of only 200-350?parts per million by volume but nearly ice-free conditions in the Northern Hemisphere and warmer-than-modern temperatures on the continents. Here we present quantitative geochemical sea surface temperature estimates from the Miocene mid-latitude North Pacific Ocean, and show that oceanic warmth persisted throughout the interval of low p(co(2)) ～12-5 Myr ago. We also present new stable isotope measurements from the western equatorial Pacific that, in conjunction with previously published data, reveal a long-term trend of thermocline shoaling in the equatorial Pacific since ～13?Myr ago. We propose that a relatively deep global thermocline, reductions in low-latitude gradients in sea surface temperature, and cloud and water vapour feedbacks may help to explain the warmth of the late Miocene. Additional shoaling of the thermocline after 5?Myr ago probably explains the stronger coupling between p(co(2)), sea surface temperatures and climate that is characteristic of the more recent Pliocene and Pleistocene epochs.     

Enhanced biological carbon consumption in a high CO2 ocean

The oceans have absorbed nearly half of the fossil-fuel carbon dioxide (CO2) emitted into the atmosphere since pre-industrial times, causing a measurable reduction in seawater pH and carbonate saturation. If CO2 emissions continue to rise at current rates, upper-ocean pH will decrease to levels lower than have existed for tens of millions of years and, critically, at a rate of change 100 times greater than at any time over this period. Recent studies have shown effects of ocean acidification on a variety of marine life forms, in particular calcifying organisms. Consequences at the community to ecosystem level, in contrast, are largely unknown. Here we show that dissolved inorganic carbon consumption of a natural plankton community maintained in mesocosm enclosures at initial CO2 partial pressures of 350, 700 and 1,050 microatm increases with rising CO2. The community consumed up to 39% more dissolved inorganic carbon at increased CO2 partial pressures compared to present levels, whereas nutrient uptake remained the same. The stoichiometry of carbon to nitrogen drawdown increased from 6.0 at low CO2 to 8.0 at high CO2, thus exceeding the Redfield carbon:nitrogen ratio of 6.6 in today's ocean. This excess carbon consumption was associated with higher loss of organic carbon from the upper layer of the stratified mesocosms. If applicable to the natural environment, the observed responses have implications for a variety of marine biological and biogeochemical processes, and underscore the importance of biologically driven feedbacks in the ocean to global change.