Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation

Understanding the composition of the atmosphere over geological time is critical to understanding the history of the Earth system, as the atmosphere is closely linked to the lithosphere, hydrosphere and biosphere. Although much of the history of the lithosphere and hydrosphere is contained in rock and mineral records, corresponding information about the atmosphere is scarce and elusive owing to the lack of direct records. Geologists have used sedimentary minerals, fossils and geochemical models to place constraints on the concentrations of carbon dioxide, oxygen or methane in the past. Here we show that the triple oxygen isotope composition of sulphate from ancient evaporites and barites shows variable negative oxygen-17 isotope anomalies over the past 750 million years. We propose that these anomalies track those of atmospheric oxygen and in turn reflect the partial pressure of carbon dioxide (P(CO2)) in the past through a photochemical reaction network linking stratospheric ozone to carbon dioxide and to oxygen. Our results suggest that P(CO2) was much higher in the early Cambrian than in younger eras, agreeing with previous modelling results. We also find that the (17)O isotope anomalies of barites from Marinoan (approximately 635 million years ago) cap carbonates display a distinct negative spike (around -0.70 per thousand), suggesting that by the time barite was precipitating in the immediate aftermath of a Neoproterozoic global glaciation, the P(CO2) was at its highest level in the past 750 million years. Our finding is consistent with the 'snowball Earth' hypothesis and/or a massive methane release after the Marinoan glaciation.     

Atmospheric carbon dioxide concentrations before 2.2 billion years ago

The composition of the Earth's early atmosphere is a subject of continuing debate. In particular, it has been suggested that elevated concentrations of atmospheric carbon dioxide would have been necessary to maintain normal surface temperatures in the face of lower solar luminosity in early Earth history. Fossil weathering profiles, known as palaeosols, have provided semi-quantitative constraints on atmospheric oxygen partial pressure (pO2) before 2.2 Gyr ago. Here we use the same well studied palaeosols to constrain atmospheric pCO2 between 2.75 and 2.2 Gyr ago. The observation that iron lost from the tops of these profiles was reprecipitated lower down as iron silicate minerals, rather than as iron carbonate, indicates that atmospheric pCO2 must have been less than 10(-1.4) atm--about 100 times today's level of 360 p.p.m., and at least five times lower than that required in one-dimensional climate models to compensate for lower solar luminosity at 2.75 Gyr. Our results suggest that either the Earth's early climate was much more sensitive to increases in pCO2 than has been thought, or that one or more greenhouse gases other than CO2 contributed significantly to the atmosphere's radiative balance during the late Archaean and early Proterozoic eons.     

A 'snowball Earth' climate triggered by continental break-up through changes in runoff

Geological and palaeomagnetic studies indicate that ice sheets may have reached the Equator at the end of the Proterozoic eon, 800 to 550 million years ago, leading to the suggestion of a fully ice-covered 'snowball Earth'. Climate model simulations indicate that such a snowball state for the Earth depends on anomalously low atmospheric carbon dioxide concentrations, in addition to the Sun being 6 per cent fainter than it is today. However, the mechanisms producing such low carbon dioxide concentrations remain controversial. Here we assess the effect of the palaeogeographic changes preceding the Sturtian glacial period, 750 million years ago, on the long-term evolution of atmospheric carbon dioxide levels using the coupled climate-geochemical model GEOCLIM. In our simulation, the continental break-up of Rodinia leads to an increase in runoff and hence consumption of carbon dioxide through continental weathering that decreases atmospheric carbon dioxide concentrations by 1,320 p.p.m. This indicates that tectonic changes could have triggered a progressive transition from a 'greenhouse' to an 'icehouse' climate during the Neoproterozoic era. When we combine these results with the concomitant weathering effect of the voluminous basaltic traps erupted throughout the break-up of Rodinia, our simulation results in a snowball glaciation.     

High levels of atmospheric carbon dioxide necessary for the termination of global glaciation

The possibility that the Earth suffered episodes of global glaciation as recently as the Neoproterozoic period, between about 900 and 543 million years ago, has been widely discussed. Termination of such 'hard snowball Earth' climate states has been proposed to proceed from accumulation of carbon dioxide in the atmosphere. Many salient aspects of the snowball scenario depend critically on the threshold of atmospheric carbon dioxide concentrations needed to trigger deglaciation. Here I present simulations with a general circulation model, using elevated carbon dioxide levels to estimate this deglaciation threshold. The model simulates several phenomena that are expected to be significant in a 'snowball Earth' scenario, but which have not been considered in previous studies with less sophisticated models, such as a reduction of vertical temperature gradients in winter, a reduction in summer tropopause height, the effect of snow cover and a reduction in cloud greenhouse effects. In my simulations, the system remains far short of deglaciation even at atmospheric carbon dioxide concentrations of 550 times the present levels (0.2 bar of CO2). I find that at much higher carbon dioxide levels, deglaciation is unlikely unless unknown feedback cycles that are not captured in the model come into effect.     

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.     

The life span of the biosphere revisited

A decade ago, Lovelock and Whitfield raised the question of how much longer the biosphere can survive on Earth. They pointed out that, despite the current fossil-fuel induced increase in the atmospheric CO2 concentration, the long-term trend should be in the opposite direction: as increased solar luminosity warms the Earth, silicate rocks should weather more readily, causing atmospheric CO2 to decrease. In their model, atmospheric CO2 falls below the critical level for C3 photosynthesis, 150 parts per million (p.p.m.), in only 100 Myr, and this is assumed to mark the demise of the biosphere as a whole. Here, we re-examine this problem using a more elaborate model that includes a more accurate treatment of the greenhouse effect of CO2, a biologically mediated weathering parameterization, and the realization that C4 photosynthesis can persist to much lower concentrations of atmospheric CO2(<10 p.p.m.). We find that a C4-plant-based biosphere could survive for at least another 0.9 Gyr to 1.5 Gyr after the present time, depending respectively on whether CO2 or temperature is the limiting factor. Within an additional 1 Gyr, Earth may lose its water to space, thereby following the path of its sister planet, Venus.     

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.     

Thresholds for Cenozoic bipolar glaciation

The long-standing view of Earth's Cenozoic glacial history calls for the first continental-scale glaciation of Antarctica in the earliest Oligocene epoch ( approximately 33.6 million years ago), followed by the onset of northern-hemispheric glacial cycles in the late Pliocene epoch, about 31 million years later. The pivotal early Oligocene event is characterized by a rapid shift of 1.5 parts per thousand in deep-sea benthic oxygen-isotope values (Oi-1) within a few hundred thousand years, reflecting a combination of terrestrial ice growth and deep-sea cooling. The apparent absence of contemporaneous cooling in deep-sea Mg/Ca records, however, has been argued to reflect the growth of more ice than can be accommodated on Antarctica; this, combined with new evidence of continental cooling and ice-rafted debris in the Northern Hemisphere during this period, raises the possibility that Oi-1 represents a precursory bipolar glaciation. Here we test this hypothesis using an isotope-capable global climate/ice-sheet model that accommodates both the long-term decline of Cenozoic atmospheric CO(2) levels and the effects of orbital forcing. We show that the CO(2) threshold below which glaciation occurs in the Northern Hemisphere ( approximately 280 p.p.m.v.) is much lower than that for Antarctica ( approximately 750 p.p.m.v.). Therefore, the growth of ice sheets in the Northern Hemisphere immediately following Antarctic glaciation would have required rapid CO(2) drawdown within the Oi-1 timeframe, to levels lower than those estimated by geochemical proxies and carbon-cycle models. Instead of bipolar glaciation, we find that Oi-1 is best explained by Antarctic glaciation alone, combined with deep-sea cooling of up to 4 degrees C and Antarctic ice that is less isotopically depleted (-30 to -35 per thousand) than previously suggested. Proxy CO(2) estimates remain above our model's northern-hemispheric glaciation threshold of approximately 280 p.p.m.v. until approximately 25 Myr ago, but have been near or below that level ever since. This implies that episodic northern-hemispheric ice sheets have been possible some 20 million years earlier than currently assumed (although still much later than Oi-1) and could explain some of the variability in Miocene sea-level records.     

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.     

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.     

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.     

A 300-million-year record of atmospheric carbon dioxide from fossil plant cuticles

To understand better the link between atmospheric CO2 concentrations and climate over geological time, records of past CO2 are reconstructed from geochemical proxies. Although these records have provided us with a broad picture of CO2 variation throughout the Phanerozoic eon (the past 544 Myr), inconsistencies and gaps remain that still need to be resolved. Here I present a continuous 300-Myr record of stomatal abundance from fossil leaves of four genera of plants that are closely related to the present-day Ginkgo tree. Using the known relationship between leaf stomatal abundance and growing season CO2 concentrations, I reconstruct past atmospheric CO2 concentrations. For the past 300 Myr, only two intervals of low CO2 (<1,000 p.p.m.v.) are inferred, both of which coincide with known ice ages in Neogene (1-8 Myr) and early Permian (275-290 Myr) times. But for most of the Mesozoic era (65-250 Myr), CO2 levels were high (1,000-2,000 p.p.m.v.), with transient excursions to even higher CO2 (>2,000 p.p.m.v.) concentrations. These results are consistent with some reconstructions of past CO2 (refs 1, 2) and palaeotemperature records, but suggest that CO2 reconstructions based on carbon isotope proxies may be compromised by episodic outbursts of isotopically light methane. These results support the role of water vapour, methane and CO2 in greenhouse climate warming over the past 300 Myr.     

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.     

Acceleration of global warming due to carbon-cycle feedbacks in a coupled climate model

The continued increase in the atmospheric concentration of carbon dioxide due to anthropogenic emissions is predicted to lead to significant changes in climate. About half of the current emissions are being absorbed by the ocean and by land ecosystems, but this absorption is sensitive to climate as well as to atmospheric carbon dioxide concentrations, creating a feedback loop. General circulation models have generally excluded the feedback between climate and the biosphere, using static vegetation distributions and CO2 concentrations from simple carbon-cycle models that do not include climate change. Here we present results from a fully coupled, three-dimensional carbon-climate model, indicating that carbon-cycle feedbacks could significantly accelerate climate change over the twenty-first century. We find that under a 'business as usual' scenario, the terrestrial biosphere acts as an overall carbon sink until about 2050, but turns into a source thereafter. By 2100, the ocean uptake rate of 5 Gt C yr(-1) is balanced by the terrestrial carbon source, and atmospheric CO2 concentrations are 250 p.p.m.v. higher in our fully coupled simulation than in uncoupled carbon models, resulting in a global-mean warming of 5.5 K, as compared to 4 K without the carbon-cycle feedback.     

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.     

Snowball Earth prevention by dissolved organic carbon remineralization

The 'snowball Earth' hypothesis posits the occurrence of a sequence of glaciations in the Earth's history sufficiently deep that photosynthetic activity was essentially arrested. Because the time interval during which these events are believed to have occurred immediately preceded the Cambrian explosion of life, the issue as to whether such snowball states actually developed has important implications for our understanding of evolutionary biology. Here we couple an explicit model of the Neoproterozoic carbon cycle to a model of the physical climate system. We show that the drawdown of atmospheric oxygen into the ocean, as surface temperatures decline, operates so as to increase the rate of remineralization of a massive pool of dissolved organic carbon. This leads directly to an increase of atmospheric carbon dioxide, enhanced greenhouse warming of the surface of the Earth, and the prevention of a snowball state.     

Methane seeps, methane hydrate destabilization, and the late Neoproterozoic postglacial cap carbonates

Natural gas (methane) hydrates, the crystalline solids composed mainly of methane and water, are present in marine sediments of the continental margins and polar permafrost under a delicate balance of temperature (< 7℃) and hydrostatic pressure (> 50×10…     

Air density 2.7 billion years ago limited to less than twice modern levels by fossil raindrop imprints

According to the 'Faint Young Sun' paradox, during the late Archaean eon a Sun approximately 20% dimmer warmed the early Earth such that it had liquid water and a clement climate. Explanations for this phenomenon have invoked a denser atmosphere that provided warmth by nitrogen pressure broadening or enhanced greenhouse gas concentrations. Such solutions are allowed by geochemical studies and numerical investigations that place approximate concentration limits on Archaean atmospheric gases, including methane, carbon dioxide and oxygen. But no field data constraining ground-level air density and barometric pressure have been reported, leaving the plausibility of these various hypotheses in doubt. Here we show that raindrop imprints in tuffs of the Ventersdorp Supergroup, South Africa, constrain surface air density 2.7 billion years ago to less than twice modern levels. We interpret the raindrop fossils using experiments in which water droplets of known size fall at terminal velocity into fresh and weathered volcanic ash, thus defining a relationship between imprint size and raindrop impact momentum. Fragmentation following raindrop flattening limits raindrop size to a maximum value independent of air density, whereas raindrop terminal velocity varies as the inverse of the square root of air density. If the Archaean raindrops reached the modern maximum measured size, air density must have been less than 2.3?kg?m(-3), compared to today's 1.2?kg?m(-3), but because such drops rarely occur, air density was more probably below 1.3?kg?m(-3). The upper estimate for air density renders the pressure broadening explanation possible, but it is improbable under the likely lower estimates. Our results also disallow the extreme CO(2) levels required for hot Archaean climates.     

Carbon dioxide degassing flux from two geothermal fields in Tibet,China

Over geological time scales,Earth degassing has a significant impact on atmospheric carbon dioxide(CO2) concentrations,which are an important component of global carbon cycle models.In Tibet,structural conditions and associated widespread geothermal systems lead to carbon dioxide degassing during geothermal water migration.We characterized the hydrochemical conditions of two geothermal fields on the Tibetan Plateau.The chemical composition of geothermal waters was controlled by K-feldspar and albite.Geother...     

High CO2 levels in the Proterozoic atmosphere estimated from analyses of individual microfossils

Solar luminosity on the early Earth was significantly lower than today. Therefore, solar luminosity models suggest that, in the atmosphere of the early Earth, the concentration of greenhouse gases such as carbon dioxide and methane must have been much higher. However, empirical estimates of Proterozoic levels of atmospheric carbon dioxide concentrations have not hitherto been available. Here we present ion microprobe analyses of the carbon isotopes in individual organic-walled microfossils extracted from a Proterozoic ( approximately 1.4-gigayear-old) shale in North China. Calculated magnitudes of the carbon isotope fractionation in these large, morphologically complex microfossils suggest elevated levels of carbon dioxide in the ancient atmosphere--between 10 and 200 times the present atmospheric level. Our results indicate that carbon dioxide was an important greenhouse gas during periods of lower solar luminosity, probably dominating over methane after the atmosphere and hydrosphere became pervasively oxygenated between 2 and 2.2 gigayears ago.