Isotopic evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry

The evolution of the Earth's atmosphere is marked by a transition from an early atmosphere with very low oxygen content to one with an oxygen content within a few per cent of the present atmospheric level. Placing time constraints on this transition is of interest because it identifies the time when oxidative weathering became efficient, when ocean chemistry was transformed by delivery of oxygen and sulphate, and when a large part of Earth's ecology changed from anaerobic to aerobic. The observation of non-mass-dependent sulphur isotope ratios in sedimentary rocks more than approximately 2.45 billion years (2.45 Gyr) old and the disappearance of this signal in younger sediments is taken as one of the strongest lines of evidence for the transition from an anoxic to an oxic atmosphere around 2.45 Gyr ago. Detailed examination of the sulphur isotope record before 2.45 Gyr ago also reveals early and late periods of large amplitude non-mass-dependent signals bracketing an intervening period when the signal was attenuated. Until recently, this record has been too sparse to allow interpretation, but collection of new data has prompted some workers to argue that the Mesoarchaean interval (3.2-2.8 Gyr ago) lacks a non-mass-dependent signal, and records the effects of earlier and possibly permanent oxygenation of the Earth's atmosphere. Here we focus on the Mesoarchaean interval, and demonstrate preservation of a non-mass-dependent signal that differs from that of preceding and following periods in the Archaean. Our findings point to the persistence of an anoxic early atmosphere, and identify variability within the isotope record that suggests changes in pre-2.45-Gyr-ago atmospheric pathways for non-mass-dependent chemistry and in the ultraviolet transparency of an evolving early atmosphere.     

146Sm-142Nd evidence from Isua metamorphosed sediments for early differentiation of the Earth's mantle

Application of the 147Sm-143Nd chronometer (half-life of 106 Gyr) suggests that large-scale differentiation of the Earth's mantle may have occurred during the first few hundred million years of its history. However, the signature of mantle depletion found in early Archaean rocks is often obscured by uncertainties resulting from open-system behaviour of the rocks during later high-grade metamorphic events. Hence, although strong hints exist regarding the presence of differentiated silicate reservoirs before 4.0 Gyr ago, both the nature and age of early mantle differentiation processes remain largely speculative. Here we apply short-lived 146Sm-142Nd chronometry (half-life of 103 Myr) to early Archaean rocks using ultraprecise measurement of Nd isotope ratios. The analysed samples are well-preserved metamorphosed sedimentary rocks from the 3.7-3.8-Gyr Isua greenstone belt of West Greenland. Our coupled isotopic calculations, combined with an initial epsilon 143Nd value from ref. 6, constrain the mean age of mantle differentiation to 4,460 +/- 115 Myr. This early Sm/Nd fractionation probably reflects differentiation of the Earth's mantle during the final stage of terrestrial accretion.     

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.     

Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago

Earth's lithosphere probably experienced an evolution towards the modern plate tectonic regime, owing to secular changes in mantle temperature. Radiogenic isotope variations are interpreted as evidence for the declining rates of continental crustal growth over time, with some estimates suggesting that over 70% of the present continental crustal reservoir was extracted by the end of the Archaean eon. Patterns of crustal growth and reworking in rocks younger than three billion years (Gyr) are thought to reflect the assembly and break-up of supercontinents by Wilson cycle processes and mark an important change in lithosphere dynamics. In southern West Greenland numerous studies have, however, argued for subduction settings and crust growth by arc accretion back to 3.8 Gyr ago, suggesting that modern-day tectonic regimes operated during the formation of the earliest crustal rock record. Here we report in situ uranium-lead, hafnium and oxygen isotope data from zircons of basement rocks in southern West Greenland across the critical time period during which modern-like tectonic regimes could have initiated. Our data show pronounced differences in the hafnium isotope-time patterns across this interval, requiring changes in the characteristics of the magmatic protolith. The observations suggest that 3.9-3.5-Gyr-old rocks differentiated from a >3.9-Gyr-old source reservoir with a chondritic to slightly depleted hafnium isotope composition. In contrast, rocks formed after 3.2 Gyr ago register the first additions of juvenile depleted material (that is, new mantle-derived crust) since 3.9 Gyr ago, and are characterized by striking shifts in hafnium isotope ratios similar to those shown by Phanerozoic subduction-related orogens. These data suggest a transitional period 3.5-3.2 Gyr ago from an ancient (3.9-3.5 Gyr old) crustal evolutionary regime unlike that of modern plate tectonics to a geodynamic setting after 3.2 Gyr ago that involved juvenile crust generation by plate tectonic processes.     

Sulphur isotope evidence for an oxic Archaean atmosphere

The presence of mass-independently fractionated sulphur isotopes (MIF-S) in many sedimentary rocks older than approximately 2.4 billion years (Gyr), and the absence of MIF-S in younger rocks, has been considered the best evidence for a dramatic change from an anoxic to oxic atmosphere around 2.4 Gyr ago. This is because the only mechanism known to produce MIF-S has been ultraviolet photolysis of volcanic sulphur dioxide gas in an oxygen-poor atmosphere. Here we report the absence of MIF-S throughout approximately 100-m sections of 2.76-Gyr-old lake sediments and 2.92-Gyr-old marine shales in the Pilbara Craton, Western Australia. We propose three possible interpretations of the MIF-S geologic record: (1) the level of atmospheric oxygen fluctuated greatly during the Archaean era; (2) the atmosphere has remained oxic since approximately 3.8 Gyr ago, and MIF-S in sedimentary rocks represents times and regions of violent volcanic eruptions that ejected large volumes of sulphur dioxide into the stratosphere; or (3) MIF-S in rocks was mostly created by non-photochemical reactions during sediment diagenesis, and thus is not linked to atmospheric chemistry.     

A possible nitrogen crisis for Archaean life due to reduced nitrogen fixation by lightning.

Nitrogen is an essential element for life and is often the limiting nutrient for terrestrial ecosystems. As most nitrogen is locked in the kinetically stable form, N2, in the Earth's atmosphere, processes that can fix N2 into biologically available forms-such as nitrate and ammonia-control the supply of nitrogen for organisms. On the early Earth, nitrogen is thought to have been fixed abiotically, as nitric oxide formed during lightning discharge. The advent of biological nitrogen fixation suggests that at some point the demand for fixed nitrogen exceeded the supply from abiotic sources, but the timing and causes of the onset of biological nitrogen fixation remain unclear. Here we report an experimental simulation of nitrogen fixation by lightning over a range of Hadean (4.5-3.8 Gyr ago) and Archaean (3.8-2.5 Gyr ago) atmospheric compositions, from predominantly carbon dioxide to predominantly dinitrogen (but always without oxygen). We infer that, as atmospheric CO2 decreased over the Archaean period, the production of nitric oxide from lightning discharge decreased by two orders of magnitude until about 2.2 Gyr. After this time, the rise in oxygen (or methane) concentrations probably initiated other abiotic sources of nitrogen. Although the temporary reduction in nitric oxide production may have lasted for only 100 Myr or less, this was potentially long enough to cause an ecological crisis that triggered the development of biological nitrogen fixation.     

Hf-Nd isotope evidence for a transient dynamic regime in the early terrestrial mantle

Modern basalts have seemingly lost all 'memory' of the primitive Earth's mantle except for an ambiguous isotopic signal observed in some rare gases. Although the Earth is expected to have reached a thermal steady state within several hundred million years of accretion, it is not known how and when the initial chemical fractionations left over from planetary accretion (and perhaps a stage involving a magma ocean) were overshadowed by fractionations imposed by modern-style geodynamics. Because of the lack of samples older than 4 Gyr, this early dynamic regime of the Earth is poorly understood. Here we compare published Hf-Nd isotope data on supracrustals from Isua, Greenland, with similar data on lunar rocks and the SNC (martian) meteorites, and show that, about 3.8 Gyr ago, the geochemical signature of the Archaean mantle was partly inherited from the initial differentiation of the Earth. The observed features seem to indicate that the planet at that time was still losing a substantial amount of primordial heat. The survival of remnants from an early layering in the modern deep mantle may account for some unexplained seismological, thermal and geochemical characteristics of the Earth as observed today.     

Record of mid-Archaean subduction from metamorphism in the Barberton terrain, South Africa

Although plate tectonics is the central geological process of the modern Earth, its form and existence during the Archaean era (4.0-2.5 Gyr ago) are disputed. The existence of subduction during this time is particularly controversial because characteristic subduction-related mineral assemblages, typically documenting apparent geothermal gradients of 15 degrees C km(-1) or less, have not yet been recorded from in situ Archaean rocks (the lowest recorded apparent geothermal gradients are greater than 25 degrees C km(-1)). Despite this absence from the rock record, low Archaean geothermal gradients are suggested by eclogitic nodules in kimberlites and circumstantial evidence for subduction processes, including possible accretion-related structures, has been reported in Archaean terrains. The lack of spatially and temporally well-constrained high-pressure, low-temperature metamorphism continues, however, to cast doubt on the relevance of subduction-driven tectonics during the first 1.5 Gyr of the Earth's history. Here we report garnet-albite-bearing mineral assemblages that record pressures of 1.2-1.5 GPa at temperatures of 600-650 degrees C from supracrustal amphibolites from the mid-Archaean Barberton granitoid-greenstone terrain. These conditions point to apparent geothermal gradients of 12-15 degrees C-similar to those found in recent subduction zones-that coincided with the main phase of terrane accretion in the structurally overlying Barberton greenstone belt. These high-pressure, low-temperature conditions represent metamorphic evidence for cold and strong lithosphere, as well as subduction-driven tectonic processes, during the evolution of the early Earth.     

Low marine sulphate and protracted oxygenation of the Proterozoic biosphere

Progressive oxygenation of the Earth's early biosphere is thought to have resulted in increased sulphide oxidation during continental weathering, leading to a corresponding increase in marine sulphate concentration. Accurate reconstruction of marine sulphate reservoir size is therefore important for interpreting the oxygenation history of early Earth environments. Few data, however, specifically constrain how sulphate concentrations may have changed during the Proterozoic era (2.5-0.54 Gyr ago). Prior to 2.2 Gyr ago, when oxygen began to accumulate in the Earth's atmosphere, sulphate concentrations are inferred to have been <1 mM and possibly <200 microM, on the basis of limited isotopic variability preserved in sedimentary sulphides and experimental data showing suppressed isotopic fractionation at extremely low sulphate concentrations. By 0.8 Gyr ago, oxygen and thus sulphate levels may have risen significantly. Here we report large stratigraphic variations in the sulphur isotope composition of marine carbonate-associated sulphate, and use a rate-dependent model for sulphur isotope change that allows us to track changes in marine sulphate concentrations throughout the Proterozoic. Our calculations indicate sulphate levels between 1.5 and 4.5 mM, or 5-15 per cent of modern values, for more than 1 Gyr after initial oxygenation of the Earth's biosphere. Persistence of low oceanic sulphate demonstrates the protracted nature of Earth's oxygenation. It links biospheric evolution to temporal patterns in the depositional behaviour of marine iron- and sulphur-bearing minerals, biological cycling of redox-sensitive elements and availability of trace metals essential to eukaryotic development.     

Trace-element fractionation in Hadean mantle generated by melt segregation from a magma ocean

Calculations of the energetics of terrestrial accretion indicate that the Earth was extensively molten in its early history. Examination of early Archaean rocks from West Greenland (3.6-3.8 Gyr old) using short-lived 146Sm-142Nd chronometry indicates that an episode of mantle differentiation took place close to the end of accretion (4.46 +/- 0.11 Gyr ago). This has produced a chemically depleted mantle with an Sm/Nd ratio higher than the chondritic value. In contrast, application of 176Lu-176Hf systematics to 3.6-3.8-Gyr-old zircons from West Greenland indicates derivation from a mantle source with a chondritic Lu/Hf ratio. Although an early Sm/Nd fractionation could be explained by basaltic crust formation, magma ocean crystallization or formation of continental crust, the absence of coeval Lu/Hf fractionation is in sharp contrast with the well-known covariant behaviour of Sm/Nd and Lu/Hf ratios in crustal formation processes. Here we show using mineral-melt partitioning data for high-pressure mantle minerals that the observed Nd and Hf signatures could have been produced by segregation of melt from a crystallizing magma ocean at upper-mantle pressures early in Earth's history. This residual melt would have risen buoyantly and ultimately formed the earliest terrestrial protocrust.     

Oxygen-isotope evidence from ancient zircons for liquid water at the Earth's surface 4,300 Myr ago

Granitoid gneisses and supracrustal rocks that are 3,800-4,000 Myr old are the oldest recognized exposures of continental crust. To obtain insight into conditions at the Earth's surface more than 4 Gyr ago requires the analysis of yet older rocks or their mineral remnants. Such an opportunity is presented by detrital zircons more than 4 Gyr old found within 3-Gyr-old quartzitic rocks in the Murchison District of Western Australia. Here we report in situ U-Pb and oxygen isotope results for such zircons that place constraints on the age and composition of their sources and may therefore provide information about the nature of the Earth's early surface. We find that 3,910-4,280 Myr old zircons have oxygen isotope (delta18O) values ranging from 5.4+/-0.6% to 15.0+/-0.4%. On the basis of these results, we postulate that the approximately 4,300-Myr-old zircons formed from magmas containing a significant component of re-worked continental crust that formed in the presence of water near the Earth's surface. These data are therefore consistent with the presence of a hydrosphere interacting with the crust by 4,300 Myr ago.     

Aerobic respiration in the Archaean?

The Earth's atmosphere during the Archaean era (3,800-2,500 Myr ago) is generally thought to have been anoxic, with the partial pressure of atmospheric oxygen about 10(-12) times the present value. In the absence of aerobic consumption of oxygen produced by photosynthesis in the ocean, the major sink for this oxygen would have been oxidation of dissolved Fe(II). Atmospheric oxygen would also be removed by the oxidation of biogenic methane. But even very low estimates of global primary productivity, obtained from the amounts of organic carbon preserved in Archaean rocks, seem to require the sedimentation of an unrealistically large amount of iron and the oxidation of too much methane if global anoxia was to be maintained. I therefore suggest that aerobic respiration must have developed early in the Archaean to prevent a build-up of atmospheric oxygen before the Proterozoic. An atmosphere that contained a low (0.2-0.4%) but stable proportion of oxygen is required.     

Reassessing the first appearance of eukaryotes and cyanobacteria

The evolution of oxygenic photosynthesis had a profound impact on the Earth's surface chemistry, leading to a sharp rise in atmospheric oxygen between 2.45 and 2.32 billion years (Gyr) ago and the onset of extreme ice ages. The oldest widely accepted evidence for oxygenic photosynthesis has come from hydrocarbons extracted from approximately 2.7-Gyr-old shales in the Pilbara Craton, Australia, which contain traces of biomarkers (molecular fossils) indicative of eukaryotes and suggestive of oxygen-producing cyanobacteria. The soluble hydrocarbons were interpreted to be indigenous and syngenetic despite metamorphic alteration and extreme enrichment (10-20 per thousand) of (13)C relative to bulk sedimentary organic matter. Here we present micrometre-scale, in situ (13)C/(12)C measurements of pyrobitumen (thermally altered petroleum) and kerogen from these metamorphosed shales, including samples that originally yielded biomarkers. Our results show that both kerogen and pyrobitumen are strongly depleted in (13)C, indicating that indigenous petroleum is 10-20 per thousand lighter than the extracted hydrocarbons. These results are inconsistent with an indigenous origin for the biomarkers. Whatever their origin, the biomarkers must have entered the rock after peak metamorphism approximately 2.2 Gyr ago and thus do not provide evidence for the existence of eukaryotes and cyanobacteria in the Archaean eon. The oldest fossil evidence for eukaryotes and cyanobacteria therefore reverts to 1.78-1.68 Gyr ago and approximately 2.15 Gyr ago, respectively. Our results eliminate the evidence for oxygenic photosynthesis approximately 2.7 Gyr ago and exclude previous biomarker evidence for a long delay (approximately 300 million years) between the appearance of oxygen-producing cyanobacteria and the rise in atmospheric oxygen 2.45-2.32 Gyr ago.     

Early oxygenation of the terrestrial environment during the Mesoproterozoic

Geochemical data from ancient sedimentary successions provide evidence for the progressive evolution of Earth's atmosphere and oceans. Key stages in increasing oxygenation are postulated for the Palaeoproterozoic era (～2.3?billion years ago, Gyr ago) and the late Proterozoic eon (about 0.8?Gyr ago), with the latter implicated in the subsequent metazoan evolutionary expansion. In support of this rise in oxygen concentrations, a large database shows a marked change in the bacterially mediated fractionation of seawater sulphate to sulphide of Δ(34)S?相似文献   

Geomagnetic intensity variations over the past 780 kyr obtained from near-seafloor magnetic anomalies

Knowledge of past variations in the intensity of the Earth's magnetic field provides an important constraint on models of the geodynamo. A record of absolute palaeointensity for the past 50 kyr has been compiled from archaeomagnetic and volcanic materials, and relative palaeointensities over the past 800 kyr have been obtained from sedimentary sequences. But a long-term record of geomagnetic intensity should also be carried by the thermoremanence of the oceanic crust Here we show that near-seafloor magnetic anomalies recorded over the southern East Pacific Rise are well correlated with independent estimates of geomagnetic intensity during the past 780 kyr. Moreover, the pattern of absolute palaeointensity of seafloor glass samples from the same area agrees with the well-documented dipole intensity pattern for the past 50 kyr. A comparison of palaeointensities derived from seafloor glass samples with global intensity variations thus allows us to estimate the ages of surficial lava flows in this region. The record of geomagnetic intensity preserved in the oceanic crust should provide a higher-time-resolution record of crustal accretion processes at mid-ocean ridges than has previously been obtainable.     

Evidence from fluid inclusions for microbial methanogenesis in the early Archaean era

Methanogenic microbes may be one of the most primitive organisms, although it is uncertain when methanogens first appeared on Earth. During the Archaean era (before 2.5 Gyr ago), methanogens may have been important in regulating climate, because they could have provided sufficient amounts of the greenhouse gas methane to mitigate a severely frozen condition that could have resulted from lower solar luminosity during these times. Nevertheless, no direct geological evidence has hitherto been available in support of the existence of methanogens in the Archaean period, although circumstantial evidence is available in the form of approximately 2.8-Gyr-old carbon-isotope-depleted kerogen. Here we report crushing extraction and carbon isotope analysis of methane-bearing fluid inclusions in approximately 3.5-Gyr-old hydrothermal precipitates from Pilbara craton, Australia. Our results indicate that the extracted fluids contain microbial methane with carbon isotopic compositions of less than -56 per thousand included within original precipitates. This provides the oldest evidence of methanogen (> 3.46 Gyr ago), pre-dating previous geochemical evidence by about 700 million years.     

Reassessing the evidence for the earliest traces of life

The isotopic composition of graphite is commonly used as a biomarker in the oldest (>3.5 Gyr ago) highly metamorphosed terrestrial rocks. Earlier studies on isotopic characteristics of graphite occurring in rocks of the approximately 3.8-Gyr-old Isua supracrustal belt (ISB) in southern West Greenland have suggested the presence of a vast microbial ecosystem in the early Archean. This interpretation, however, has to be approached with extreme care. Here we show that graphite occurs abundantly in secondary carbonate veins in the ISB that are formed at depth in the crust by injection of hot fluids reacting with older crustal rocks (metasomatism). During these reactions, graphite forms from the disproportionation of Fe(II)-bearing carbonates at high temperature. These metasomatic rocks, which clearly lack biological relevance, were earlier thought to be of sedimentary origin and their graphite association provided the basis for inferences about early life. The new observations thus call for a reassessment of previously presented evidence for ancient traces of life in the highly metamorphosed Early Archaean rock record.     

Carbon isotope evidence for the stepwise oxidation of the Proterozoic environment

The oxidation of the Earth's crust and the increase in atmospheric oxygen early in Earth history have been linked to the accumulation of reduced carbon in sedimentary rocks. Trends in the carbon isotope composition of sedimentary organic carbon and carbonate show that during the Proterozoic aeon (2.5-0.54 Gyr ago) the organic carbon reservoir grew in size, relative to the carbonate reservoir. This increase, and the concomitant release of oxidizing power in the environment, occurred mostly during episodes of global rifting and orogeny.     

Statistical geochemistry reveals disruption in secular lithospheric evolution about 2.5 Gyr ago

The Earth has cooled over the past 4.5 billion years (Gyr) as a result of surface heat loss and declining radiogenic heat production. Igneous geochemistry has been used to understand how changing heat flux influenced Archaean geodynamics, but records of systematic geochemical evolution are complicated by heterogeneity of the rock record and uncertainties regarding selection and preservation bias. Here we apply statistical sampling techniques to a geochemical database of about 70,000 samples from the continental igneous rock record to produce a comprehensive record of secular geochemical evolution throughout Earth history. Consistent with secular mantle cooling, compatible and incompatible elements in basalts record gradually decreasing mantle melt fraction through time. Superimposed on this gradual evolution is a pervasive geochemical discontinuity occurring about 2.5?Gyr ago, involving substantial decreases in mantle melt fraction in basalts, and in indicators of deep crustal melting and fractionation, such as Na/K, Eu/Eu* (europium anomaly) and La/Yb ratios in felsic rocks. Along with an increase in preserved crustal thickness across the Archaean/Proterozoic boundary, these data are consistent with a model in which high-degree Archaean mantle melting produced a thick, mafic lower crust and consequent deep crustal delamination and melting--leading to abundant tonalite-trondhjemite-granodiorite magmatism and a thin preserved Archaean crust. The coincidence of the observed changes in geochemistry and crustal thickness with stepwise atmospheric oxidation at the end of the Archaean eon provides a significant temporal link between deep Earth geochemical processes and the rise of atmospheric oxygen on the Earth.     

An Archaean heavy bombardment from a destabilized extension of the asteroid belt

The barrage of comets and asteroids that produced many young lunar basins (craters over 300 kilometres in diameter) has frequently been called the Late Heavy Bombardment (LHB). Many assume the LHB ended about 3.7 to 3.8 billion years (Gyr) ago with the formation of Orientale basin. Evidence for LHB-sized blasts on Earth, however, extend into the Archaean and early Proterozoic eons, in the form of impact spherule beds: globally distributed ejecta layers created by Chicxulub-sized or larger cratering events4. At least seven spherule beds have been found that formed between 3.23 and 3.47?Gyr ago, four between 2.49 and 2.63?Gyr ago, and one between 1.7 and 2.1?Gyr ago. Here we report that the LHB lasted much longer than previously thought, with most late impactors coming from the E belt, an extended and now largely extinct portion of the asteroid belt between 1.7 and 2.1 astronomical units from Earth. This region was destabilized by late giant planet migration. E-belt survivors now make up the high-inclination Hungaria asteroids. Scaling from the observed Hungaria asteroids, we find that E-belt projectiles made about ten lunar basins between 3.7 and 4.1?Gyr ago. They also produced about 15 terrestrial basins between 2.5 and 3.7?Gyr ago, as well as around 70 and four Chicxulub-sized or larger craters on the Earth and Moon, respectively, between 1.7 and 3.7?Gyr ago. These rates reproduce impact spherule bed and lunar crater constraints.