A lithium-isotope perspective on the evolution of carbon and silicon cycles.

The evolution of the global carbon and silicon cycles is thought to have contributed to the long-term stability of Earth's climate1-3. Many questions remain, however, regarding the feedback mechanisms at play, and there are limited quantitative constraints on the sources and sinks of these elements in Earth's surface environments4-12. Here we argue that the lithium-isotope record can be used to track the processes controlling the long-term carbon and silicon cycles. By analysing more than 600 shallow-water marine carbonate samples from more than 100 stratigraphic units, we construct a new carbonate-based lithium-isotope record spanning the past 3 billion years. The data suggest an increase in the carbonate lithium-isotope values over time, which we propose was driven by long-term changes in the lithium-isotopic conditions of sea water, rather than by changes in the sedimentary alterations of older samples. Using a mass-balance modelling approach, we propose that the observed trend in lithium-isotope values reflects a transition from Precambrian carbon and silicon cycles to those characteristic of the modern. We speculate that this transition was linked to a gradual shift to a biologically controlled marine silicon cycle and the evolutionary radiation of land plants13,14.

Phanerozoic flooding of North America and the Great Unconformity.

The flooding record of North America has been used to infer patterns of global erosion and sea level in deep time. Here, we utilize the geospatial dimension of the stratigraphic record provided by the Macrostrat database, and patterns of erosion from thermochronology, to resolve local tectonic subsidence from global sea level. We show that the flooding history of North America correlates in space and time with continent-facing subduction along active margins, consistent with subduction-driven dynamic topographic subsidence of the continental interior. Nonetheless, the continentally aggregated flooding signal of North America is an exaggerated global M-curve of Phanerozoic sea level. This coincidence relates to the closing of the geodynamic loop of the supercontinent cycle: Subduction under North America accommodated both the makeup and breakup of Pangaea, which, coupled with changing ridge length, flattened hypsometry, and increased sea level both locally and globally. The sole Phanerozoic exception to this pattern of global sea level tracking North American near-field geodynamics is the Cambrian Sauk transgression. We argue that this is a far-field record of the inception of circum-Gondwanan subduction, independent of North America, which significantly flattened Earth's hypsometry. This hypsometric flattening displaced ocean water globally, flooding tectonically passive North America to seal the Great Unconformity.

The rise of New Guinea and the fall of Neogene global temperatures.

The ~2,000-km-long Central Range of New Guinea is a hotspot of modern carbon sequestration due to the chemical weathering of igneous rocks with steep topography in the warm wet tropics. These high mountains formed in a collision between the Australian plate and ophiolite-bearing volcanic arc terranes, but poor resolution of the uplift and exhumation history has precluded assessments of the impact on global climate change. Here, we develop a palinspastic reconstruction of the Central Range orogen with existing surface geological constraints and seismic data to generate time-temperature paths and estimate volumes of eroded material. New (U-Th)/He thermochronology data reveal rapid uplift and regional denudation between 10 and 6 Mya. Erosion fluxes from the palinspastic reconstruction, calibrated for time with the thermochronological data, were used as input to a coupled global climate and weathering model. This model estimates 0.6 to 1.2 °C of cooling associated with the Late Miocene rise of New Guinea due to increased silicate weathering alone, and this CO2 sink continues to the present. Our data and modeling experiments support the hypothesis that tropical arc-continent collision and the rise of New Guinea contributed to Neogene cooling due to increased silicate weathering.

Diachronous development of Great Unconformities before Neoproterozoic Snowball Earth.

The Great Unconformity marks a major gap in the continental geological record, separating Precambrian basement from Phanerozoic sedimentary rocks. However, the timing, magnitude, spatial heterogeneity, and causes of the erosional event(s) and/or depositional hiatus that lead to its development are unknown. We present field relationships from the 1.07-Ga Pikes Peak batholith in Colorado that constrain the position of Cryogenian and Cambrian paleosurfaces below the Great Unconformity. Tavakaiv sandstone injectites with an age of ≥676 ± 26 Ma cut Pikes Peak granite. Injection of quartzose sediment in bulbous bodies indicates near-surface conditions during emplacement. Fractured, weathered wall rock around Tavakaiv bodies and intensely altered basement fragments within unweathered injectites imply still earlier regolith development. These observations provide evidence that the granite was exhumed and resided at the surface prior to sand injection, likely before the 717-Ma Sturtian glaciation for the climate appropriate for regolith formation over an extensive region of the paleolandscape. The 510-Ma Sawatch sandstone directly overlies Tavakaiv-injected Pikes granite and drapes over core stones in Pikes regolith, consistent with limited erosion between 717 and 510 Ma. Zircon (U-Th)/He dates for basement below the Great Unconformity are 975 to 46 Ma and are consistent with exhumation by 717 Ma. Our results provide evidence that most erosion below the Great Unconformity in Colorado occurred before the first Neoproterozoic Snowball Earth and therefore cannot be a product of glacial erosion. We propose that multiple Great Unconformities developed diachronously and represent regional tectonic features rather than a synchronous global phenomenon.

Volcanic controls on seawater sulfate over the past 120 million years.

Changes in the geological sulfur cycle are inferred from the sulfur isotopic composition of marine barite. The structure of the 34S/32S record from the Mesozoic to present, which includes ∼50- and 100-Ma stepwise increases, has been interpreted as the result of microbial isotope effects or abrupt changes to tectonics and associated pyrite burial. Untangling the physical processes that govern the marine sulfur cycle and associated isotopic change is critical to understanding how climate, atmospheric oxygenation, and marine ecology have coevolved over geologic time. Here we demonstrate that the sulfur outgassing associated with emplacement of large igneous provinces can produce the apparent stepwise jumps in the isotopic record when coupled to long-term changes in burial efficiency. The record of large igneous provinces map onto the required outgassing events in our model, with the two largest steps in the sulfur isotope record coinciding with the emplacement of large igneous provinces into volatile-rich sedimentary basins. This solution provides a quantitative picture of the last 120 My of change in the ocean's largest oxidant reservoir.

Emergence of the Southeast Asian islands as a driver for Neogene cooling.

Steep topography, a tropical climate, and mafic lithologies contribute to efficient chemical weathering and carbon sequestration in the Southeast Asian islands. Ongoing arc-continent collision between the Sunda-Banda arc system and Australia has increased the area of subaerially exposed land in the region since the mid-Miocene. Concurrently, Earth's climate has cooled since the Miocene Climatic Optimum, leading to growth of the Antarctic ice sheet and the onset of Northern Hemisphere glaciation. We seek to evaluate the hypothesis that the emergence of the Southeast Asian islands played a significant role in driving this cooling trend through increasing global weatherability. To do so, we have compiled paleoshoreline data and incorporated them into GEOCLIM, which couples a global climate model to a silicate weathering model with spatially resolved lithology. We find that without the increase in area of the Southeast Asian islands over the Neogene, atmospheric pCO2 would have been significantly higher than preindustrial values, remaining above the levels necessary for initiating Northern Hemisphere ice sheets.

Statistical analysis of iron geochemical data suggests limited late Proterozoic oxygenation.

Sedimentary rocks deposited across the Proterozoic-Phanerozoic transition record extreme climate fluctuations, a potential rise in atmospheric oxygen or re-organization of the seafloor redox landscape, and the initial diversification of animals. It is widely assumed that the inferred redox change facilitated the observed trends in biodiversity. Establishing this palaeoenvironmental context, however, requires that changes in marine redox structure be tracked by means of geochemical proxies and translated into estimates of atmospheric oxygen. Iron-based proxies are among the most effective tools for tracking the redox chemistry of ancient oceans. These proxies are inherently local, but have global implications when analysed collectively and statistically. Here we analyse about 4,700 iron-speciation measurements from shales 2,300 to 360 million years old. Our statistical analyses suggest that subsurface water masses in mid-Proterozoic oceans were predominantly anoxic and ferruginous (depleted in dissolved oxygen and iron-bearing), but with a tendency towards euxinia (sulfide-bearing) that is not observed in the Neoproterozoic era. Analyses further indicate that early animals did not experience appreciable benthic sulfide stress. Finally, unlike proxies based on redox-sensitive trace-metal abundances, iron geochemical data do not show a statistically significant change in oxygen content through the Ediacaran and Cambrian periods, sharply constraining the magnitude of the end-Proterozoic oxygen increase. Indeed, this re-analysis of trace-metal data is consistent with oxygenation continuing well into the Palaeozoic era. Therefore, if changing redox conditions facilitated animal diversification, it did so through a limited rise in oxygen past critical functional and ecological thresholds, as is seen in modern oxygen minimum zone benthic animal communities.

Dynamics of a Snowball Earth ocean.

Geological evidence suggests that marine ice extended to the Equator at least twice during the Neoproterozoic era (about 750 to 635 million years ago), inspiring the Snowball Earth hypothesis that the Earth was globally ice-covered. In a possible Snowball Earth climate, ocean circulation and mixing processes would have set the melting and freezing rates that determine ice thickness, would have influenced the survival of photosynthetic life, and may provide important constraints for the interpretation of geochemical and sedimentological observations. Here we show that in a Snowball Earth, the ocean would have been well mixed and characterized by a dynamic circulation, with vigorous equatorial meridional overturning circulation, zonal equatorial jets, a well developed eddy field, strong coastal upwelling and convective mixing. This is in contrast to the sluggish ocean often expected in a Snowball Earth scenario owing to the insulation of the ocean from atmospheric forcing by the thick ice cover. As a result of vigorous convective mixing, the ocean temperature, salinity and density were either uniform in the vertical direction or weakly stratified in a few locations. Our results are based on a model that couples ice flow and ocean circulation, and is driven by a weak geothermal heat flux under a global ice cover about a kilometre thick. Compared with the modern ocean, the Snowball Earth ocean had far larger vertical mixing rates, and comparable horizontal mixing by ocean eddies. The strong circulation and coastal upwelling resulted in melting rates near continents as much as ten times larger than previously estimated. Although we cannot resolve the debate over the existence of global ice cover, we discuss the implications for the nutrient supply of photosynthetic activity and for banded iron formations. Our insights and constraints on ocean dynamics may help resolve the Snowball Earth controversy when combined with future geochemical and geological observations.

Low-latitude arc-continent collision as a driver for global cooling.

New constraints on the tectonic evolution of the Neo-Tethys Ocean indicate that at ∼90-70 Ma and at ∼50-40 Ma, vast quantities of mafic and ultramafic rocks were emplaced at low latitude onto continental crust within the tropical humid belt. These emplacement events correspond temporally with, and are potential agents for, the global climatic cooling events that terminated the Cretaceous Thermal Maximum and the Early Eocene Climatic Optimum. We model the temporal effects of CO2 drawdown from the atmosphere due to chemical weathering of these obducted ophiolites, and of CO2 addition to the atmosphere from arc volcanism in the Neo-Tethys, between 100 and 40 Ma. Modeled variations in net CO2-drawdown rates are in excellent agreement with contemporaneous variation of ocean bottom water temperatures over this time interval, indicating that ophiolite emplacement may have played a major role in changing global climate. We demonstrate that both the lithology of the obducted rocks (mafic/ultramafic) and a tropical humid climate with high precipitation rate are needed to produce significant consumption of CO2 Based on these results, we suggest that the low-latitude closure of ocean basins along east-west trending plate boundaries may also have initiated other long-term global cooling events, such as Middle to Late Ordovician cooling and glaciation associated with the closure of the Iapetus Ocean.

Re-Os geochronology and coupled Os-Sr isotope constraints on the Sturtian snowball Earth.

After nearly a billion years with no evidence for glaciation, ice advanced to equatorial latitudes at least twice between 717 and 635 Mya. Although the initiation mechanism of these Neoproterozoic Snowball Earth events has remained a mystery, the broad synchronicity of rifting of the supercontinent Rodinia, the emplacement of large igneous provinces at low latitude, and the onset of the Sturtian glaciation has suggested a tectonic forcing. We present unique Re-Os geochronology and high-resolution Os and Sr isotope profiles bracketing Sturtian-age glacial deposits of the Rapitan Group in northwest Canada. Coupled with existing U-Pb dates, the postglacial Re-Os date of 662.4 ± 3.9 Mya represents direct geochronological constraints for both the onset and demise of a Cryogenian glaciation from the same continental margin and suggests a 55-My duration of the Sturtian glacial epoch. The Os and Sr isotope data allow us to assess the relative weathering input of old radiogenic crust and more juvenile, mantle-derived substrate. The preglacial isotopic signals are consistent with an enhanced contribution of juvenile material to the oceans and glacial initiation through enhanced global weatherability. In contrast, postglacial strata feature radiogenic Os and Sr isotope compositions indicative of extensive glacial scouring of the continents and intense silicate weathering in a post-Snowball Earth hothouse.

Deglacial volcanism and reoxygenation in the aftermath of the Sturtian Snowball Earth.

The Cryogenian Sturtian and Marinoan Snowball Earth glaciations bracket a nonglacial interval during which Demosponge and green-algal biomarkers first appear. To understand the relationships between environmental perturbations and early animal evolution, we measured sulfur and mercury isotopes from the Datangpo Formation from South China. Hg enrichment with positive Δ199Hg excursion suggests enhanced volcanism, potentially due to depressurization of terrestrial magma chambers during deglaciation. A thick stratigraphic interval of negative Δ33Spy indicates that the nonglacial interlude was characterized by low but rising sulfate levels. Model results reveal a mechanism to produce the Δ33S anomalies down to -0.284‰ through Rayleigh distillation. We propose that extreme temperatures and anoxia contributed to the apparent delay in green algal production in the aftermath of the Sturtian glaciation and the subsequent reoxygenation of the iron-rich and sulfate-depleted ocean paved the way for evolution of animals.

Emplacement of the Franklin large igneous province and initiation of the Sturtian Snowball Earth.

During the Cryogenian (720 to 635 Ma ago) Snowball Earth glaciations, ice extended to sea level near the equator. The cause of this catastrophic failure of Earth's thermostat has been unclear, but previous geochronology has suggested a rough coincidence of glacial onset with one of the largest magmatic episodes in the geological record, the Franklin large igneous province. U-Pb geochronology on zircon and baddeleyite from sills associated with the paleo-equatorial Franklin large igneous province in Arctic Canada record rapid emplacement between 719.86 ± 0.21 and 718.61 ± 0.30 Ma ago, 0.9 to 1.6 Ma before the onset of widespread glaciation. Geologic observations and (U-Th)/He dates on Franklin sills are compatible with major post-Franklin exhumation, possibly due to development of mafic volcanic highlands on windward equatorial Laurentia and increased global weatherability. After a transient magmatic CO2 flux, long-term carbon sequestration associated with increased weatherability could have nudged Earth over the threshold for runaway ice-albedo feedback.

The tempo of Ediacaran evolution.

The rise of complex macroscopic life occurred during the Ediacaran Period, an interval that witnessed large-scale disturbances to biogeochemical systems. The current Ediacaran chronostratigraphic framework is of insufficient resolution to provide robust global correlation schemes or test hypotheses for the role of biogeochemical cycling in the evolution of complex life. Here, we present new radio-isotopic dates from Ediacaran strata that directly constrain key fossil assemblages and large-magnitude carbon cycle perturbations. These new dates and integrated global correlations demonstrate that late Ediacaran strata of South China are time transgressive and that the 575- to 550-Ma interval is marked by two large negative carbon isotope excursions: the Shuram and a younger one that ended ca. 550 Ma ago. These data calibrate the tempo of Ediacaran evolution characterized by intervals of tens of millions of years of increasing ecosystem complexity, interrupted by biological turnovers that coincide with large perturbations to the carbon cycle.

Isotopically anomalous organic carbon in the aftermath of the Marinoan snowball Earth.

Throughout most of the sedimentary record, the marine carbon cycle is interpreted as being in isotopic steady state. This is most commonly inferred via isotopic reconstructions, where two export fluxes (organic carbon and carbonate) are offset by a constant isotopic fractionation of ~25 (termed εorg-carb ). Sedimentary deposits immediately overlying the Marinoan snowball Earth diamictites, however, stray from this prediction. In stratigraphic sections from the Ol Formation (Mongolia) and Sheepbed Formation (Canada), we observe a temporary excursion where the organic matter has anomalously heavy δ13 C and is grossly decoupled from the carbonate δ13 C. This signal may reflect the unique biogeochemical conditions that persisted in the aftermath of snowball Earth. For example, physical oceanographic modeling suggests that a strong density gradient caused the ocean to remain stratified for about 50,000 years after termination of the Marinoan snowball event, during which time the surface ocean and continental weathering consumed the large atmospheric CO2 reservoir. Further, we now better understand how δ13 C records of carbonate can be post-depostionally altered and thus be misleading. In an attempt to explain the observed carbon isotope record, we developed a model that tracks the fluxes and isotopic values of carbon between the surface ocean, deep ocean, and atmosphere. By comparing the model output to the sedimentary data, stratification alone cannot generate the anomalous observed isotopic signal. Reproducing the heavy δ13 C in organic matter requires the progressively diminishing contribution of an additional anomalous source of organic matter. The exact source of this organic matter is unclear.

Arc-continent collisions in the tropics set Earth's climate state.

On multimillion-year time scales, Earth has experienced warm ice-free and cold glacial climates, but it is unknown whether transitions between these background climate states were the result of changes in carbon dioxide sources or sinks. Low-latitude arc-continent collisions are hypothesized to drive cooling by exhuming and eroding mafic and ultramafic rocks in the warm, wet tropics, thereby increasing Earth's potential to sequester carbon through chemical weathering. To better constrain global weatherability through time, the paleogeographic position of all major Phanerozoic arc-continent collisions was reconstructed and compared to the latitudinal distribution of ice sheets. This analysis reveals a strong correlation between the extent of glaciation and arc-continent collisions in the tropics. Earth's climate state is set primarily by global weatherability, which changes with the latitudinal distribution of arc-continent collisions.

The geologic history of seawater oxygen isotopes from marine iron oxides.

The oxygen isotope composition (δ18O) of marine sedimentary rocks has increased by 10 to 15 per mil since Archean time. Interpretation of this trend is hindered by the dual control of temperature and fluid δ18O on the rocks' isotopic composition. A new δ18O record in marine iron oxides covering the past ~2000 million years shows a similar secular rise. Iron oxide precipitation experiments reveal a weakly temperature-dependent iron oxide-water oxygen isotope fractionation, suggesting that increasing seawater δ18O over time was the primary cause of the long-term rise in δ18O values of marine precipitates. The 18O enrichment may have been driven by an increase in terrestrial sediment cover, a change in the proportion of high- and low-temperature crustal alteration, or a combination of these and other factors.

Snowball Earth climate dynamics and Cryogenian geology-geobiology.

Geological evidence indicates that grounded ice sheets reached sea level at all latitudes during two long-lived Cryogenian (58 and ≥5 My) glaciations. Combined uranium-lead and rhenium-osmium dating suggests that the older (Sturtian) glacial onset and both terminations were globally synchronous. Geochemical data imply that CO2 was 102 PAL (present atmospheric level) at the younger termination, consistent with a global ice cover. Sturtian glaciation followed breakup of a tropical supercontinent, and its onset coincided with the equatorial emplacement of a large igneous province. Modeling shows that the small thermal inertia of a globally frozen surface reverses the annual mean tropical atmospheric circulation, producing an equatorial desert and net snow and frost accumulation elsewhere. Oceanic ice thickens, forming a sea glacier that flows gravitationally toward the equator, sustained by the hydrologic cycle and by basal freezing and melting. Tropical ice sheets flow faster as CO2 rises but lose mass and become sensitive to orbital changes. Equatorial dust accumulation engenders supraglacial oligotrophic meltwater ecosystems, favorable for cyanobacteria and certain eukaryotes. Meltwater flushing through cracks enables organic burial and submarine deposition of airborne volcanic ash. The subglacial ocean is turbulent and well mixed, in response to geothermal heating and heat loss through the ice cover, increasing with latitude. Terminal carbonate deposits, unique to Cryogenian glaciations, are products of intense weathering and ocean stratification. Whole-ocean warming and collapsing peripheral bulges allow marine coastal flooding to continue long after ice-sheet disappearance. The evolutionary legacy of Snowball Earth is perceptible in fossils and living organisms.

Authigenic carbonate and the history of the global carbon cycle.

We present a framework for interpreting the carbon isotopic composition of sedimentary rocks, which in turn requires a fundamental reinterpretation of the carbon cycle and redox budgets over Earth's history. We propose that authigenic carbonate, produced in sediment pore fluids during early diagenesis, has played a major role in the carbon cycle in the past. This sink constitutes a minor component of the carbon isotope mass balance under the modern, high levels of atmospheric oxygen but was much larger in times of low atmospheric O(2) or widespread marine anoxia. Waxing and waning of a global authigenic carbonate sink helps to explain extreme carbon isotope variations in the Proterozoic, Paleozoic, and Triassic.

Calibrating the Cryogenian.

The Neoproterozoic was an era of great environmental and biological change, but a paucity of direct and precise age constraints on strata from this time has prevented the complete integration of these records. We present four high-precision U-Pb ages for Neoproterozoic rocks in northwestern Canada that constrain large perturbations in the carbon cycle, a major diversification and depletion in the microfossil record, and the onset of the Sturtian glaciation. A volcanic tuff interbedded with Sturtian glacial deposits, dated at 716.5 million years ago, is synchronous with the age of the Franklin large igneous province and paleomagnetic poles that pin Laurentia to an equatorial position. Ice was therefore grounded below sea level at very low paleolatitudes, which implies that the Sturtian glaciation was global in extent.