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.     

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.     

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.     

Geomagnetic field strength 3.2 billion years ago recorded by single silicate crystals

The strength of the Earth's early geomagnetic field is of importance for understanding the evolution of the Earth's deep interior, surface environment and atmosphere. Palaeomagnetic and palaeointensity data from rocks formed near the boundary of the Proterozoic and Archaean eons, some 2.5 Gyr ago, show many hallmarks of the more recent geomagnetic field. Reversals are recorded, palaeosecular variation data indicate a dipole-dominated morphology and available palaeointensity values are similar to those from younger rocks. The picture before 2.8 Gyr ago is much less clear. Rocks of the Archaean Kaapvaal craton (South Africa) are among the best-preserved, but even they have experienced low-grade metamorphism. The variable acquisition of later magnetizations by these rocks is therefore expected, precluding use of conventional palaeointensity methods. Silicate crystals from igneous rocks, however, can contain minute magnetic inclusions capable of preserving Archaean-age magnetizations. Here we use a CO2 laser heating approach and direct-current SQUID magnetometer measurements to obtain palaeodirections and intensities from single silicate crystals that host magnetite inclusions. We find 3.2-Gyr-old field strengths that are within 50 per cent of the present-day value, indicating that a viable magnetosphere sheltered the early Earth's atmosphere from solar wind erosion.     

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.     

A lower limit for atmospheric carbon dioxide levels 3.2 billion years ago

The quantification of greenhouse gases present in the Archaean atmosphere is critical for understanding the evolution of atmospheric oxygen, surface temperatures and the conditions for life on early Earth. For instance, it has been argued that small changes in the balance between two potential greenhouse gases, carbon dioxide and methane, may have dictated the feedback cycle involving organic haze production and global cooling. Climate models have focused on carbon dioxide as the greenhouse gas responsible for maintaining above-freezing surface temperatures during a time of low solar luminosity. However, the analysis of 2.75-billion-year (Gyr)-old palaeosols--soil samples preserved in the geologic record--have recently provided an upper constraint on atmospheric carbon dioxide levels well below that required in most climate models to prevent the Earth's surface from freezing. This finding prompted many to look towards methane as an additional greenhouse gas to satisfy climate models. Here we use model equilibrium reactions for weathering rinds on 3.2-Gyr-old river gravels to show that the presence of iron-rich carbonate relative to common clay minerals requires a minimum partial pressure of carbon dioxide several times higher than present-day values. Unless actual carbon dioxide levels were considerably greater than this, climate models predict that additional greenhouse gases would still need to have a role in maintaining above-freezing surface temperatures.     

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.     

The transition to a sulphidic ocean approximately 1.84 billion years ago

The Proterozoic aeon (2.5 to 0.54 billion years (Gyr) ago) marks the time between the largely anoxic world of the Archean (> 2.5 Gyr ago) and the dominantly oxic world of the Phanerozoic (< 0.54 Gyr ago). The course of ocean chemistry through the Proterozoic has traditionally been explained by progressive oxygenation of the deep ocean in response to an increase in atmospheric oxygen around 2.3 Gyr ago. This postulated rise in the oxygen content of the ocean is in turn thought to have led to the oxidation of dissolved iron, Fe(II), thus ending the deposition of banded iron formations (BIF) around 1.8 Gyr ago. An alternative interpretation suggests that the increasing atmospheric oxygen levels enhanced sulphide weathering on land and the flux of sulphate to the oceans. This increased rates of sulphate reduction, resulting in Fe(II) removal in the form of pyrite as the oceans became sulphidic. Here we investigate sediments from the approximately 1.8-Gyr-old Animikie group, Canada, which were deposited during the final stages of the main global period of BIF deposition. This allows us to evaluate the two competing hypotheses for the termination of BIF deposition. We use iron-sulphur-carbon (Fe-S-C) systematics to demonstrate continued ocean anoxia after the final global deposition of BIF and show that a transition to sulphidic bottom waters was ultimately responsible for the termination of BIF deposition. Sulphidic conditions may have persisted until a second major rise in oxygen between 0.8 to 0.58 Gyr ago, possibly reducing global rates of primary production and arresting the pace of algal evolution.     

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.     

Biomarker evidence for green and purple sulphur bacteria in a stratified Palaeoproterozoic sea

The disappearance of iron formations from the geological record approximately 1.8 billion years (Gyr) ago was the consequence of rising oxygen levels in the atmosphere starting 2.45-2.32 Gyr ago. It marks the end of a 2.5-Gyr period dominated by anoxic and iron-rich deep oceans. However, despite rising oxygen levels and a concomitant increase in marine sulphate concentration, related to enhanced sulphide oxidation during continental weathering, the chemistry of the oceans in the following mid-Proterozoic interval (approximately 1.8-0.8 Gyr ago) probably did not yet resemble our oxygen-rich modern oceans. Recent data indicate that marine oxygen and sulphate concentrations may have remained well below current levels during this period, with one model indicating that anoxic and sulphidic marine basins were widespread, and perhaps even globally distributed. Here we present hydrocarbon biomarkers (molecular fossils) from a 1.64-Gyr-old basin in northern Australia, revealing the ecological structure of mid-Proterozoic marine communities. The biomarkers signify a marine basin with anoxic, sulphidic, sulphate-poor and permanently stratified deep waters, hostile to eukaryotic algae. Phototrophic purple sulphur bacteria (Chromatiaceae) were detected in the geological record based on the new carotenoid biomarker okenane, and they seem to have co-existed with communities of green sulphur bacteria (Chlorobiaceae). Collectively, the biomarkers support mounting evidence for a long-lasting Proterozoic world in which oxygen levels remained well below modern levels.     

Geochemical evidence for terrestrial ecosystems 2.6 billion years ago

Microorganisms have flourished in the oceans since at least 3.8 billion years (3.8 Gyr) ago, but it is not at present clear when they first colonized the land. Organic matter in some Au/U-rich conglomerates and ancient soils of 2.3-2.7 Gyr age has been suggested as remnants of terrestrial organisms. Some 2.7-Gyr-old stromatolites have also been suggested as structures created by terrestrial organisms. However, it has been disputed whether this organic matter is indigenous or exogenic, and whether these stromatolites formed in marine or fresh water. Consequently, the oldest undisputed remnants of terrestrial organisms are currently the 1.2-Gyr-old microfossils from Arizona, USA. Unusually carbonaceous ancient soils--palaeosols--have been found in the Mpumalanga Province (Eastern Transvaal) of South Africa. Here we report the occurrences, elemental ratios (C, H, N, P) and isotopic compositions of this organic matter and its host rocks. These data show that the organic matter very probably represents remnants of microbial mats that developed on the soil surface between 2.6 and 2.7 Gyr ago. This places the development of terrestrial biomass more than 1.4 billion years earlier than previously reported.     

Boron and oxygen isotope evidence for recycling of subducted components over the past 2.5 Gyr

Evidence for the deep recycling of surficial materials through the Earth's mantle and their antiquity has long been sought to understand the role of subducting plates and plumes in mantle convection. Radiogenic isotope evidence for such recycling remains equivocal because the age and location of parent-daughter fractionation are not known. Conversely, while stable isotopes can provide irrefutable evidence for low-temperature fractionation, their range in most unaltered oceanic basalts is limited and the age of any variation is unconstrained. Here we show that delta(18)O ratios in basalts from the Azores are often lower than in pristine mantle. This, combined with increased Nb/B ratios and a large range in delta(11)B ratios, provides compelling evidence for the recycling of materials that had undergone fractionation near the Earth's surface. Moreover, delta(11)B is negatively correlated with (187)Os/(188)Os ratios, which extend to subchondritic values, constraining the age of the high Nb/B, (11)B-enriched endmember to be more than 2.5 billion years (Gyr) old. We infer this component to be melt- and fluid-depleted lithospheric mantle from a subducted oceanic plate, whereas other Azores basalts contain a contribution from approximately 3-Gyr-old melt-enriched basalt. We conclude that both components are most probably derived from an Archaean oceanic plate that was subducted, arguably into the deep mantle, where it was stored until thermal buoyancy caused it to rise beneath the Azores islands approximately 3 Gyr later.     

Dating the rise of atmospheric oxygen

Several lines of geological and geochemical evidence indicate that the level of atmospheric oxygen was extremely low before 2.45 billion years (Gyr) ago, and that it had reached considerable levels by 2.22 Gyr ago. Here we present evidence that the rise of atmospheric oxygen had occurred by 2.32 Gyr ago. We found that syngenetic pyrite is present in organic-rich shales of the 2.32-Gyr-old Rooihoogte and Timeball Hill formations, South Africa. The range of the isotopic composition of sulphur in this pyrite is large and shows no evidence of mass-independent fractionation, indicating that atmospheric oxygen was present at significant levels (that is, greater than 10(-5) times that of the present atmospheric level) during the deposition of these units. The presence of rounded pebbles of sideritic iron formation at the base of the Rooihoogte Formation and an extensive and thick ironstone layer consisting of haematitic pisolites and o?lites in the upper Timeball Hill Formation indicate that atmospheric oxygen rose significantly, perhaps for the first time, during the deposition of the Rooihoogte and Timeball Hill formations. These units were deposited between what are probably the second and third of the three Palaeoproterozoic glacial events.     

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.     

Tungsten isotope evidence from approximately 3.8-Gyr metamorphosed sediments for early meteorite bombardment of the Earth

The 'Late Heavy Bombardment' was a phase in the impact history of the Moon that occurred 3.8 4.0 Gyr ago, when the lunar basins with known dates were formed. But no record of this event has yet been reported from the few surviving rocks of this age on the Earth. Here we report tungsten isotope anomalies, based on the (182)Hf (182)W system (half-life of 9 Myr), in metamorphosed sedimentary rocks from the 3.7 3.8-Gyr-old Isua greenstone belt of West Greenland and closely related rocks from northern Labrador, Canada. As it is difficult to conceive of a mechanism by which tungsten isotope heterogeneities could have been preserved in the Earth's dynamic crust mantle environment from a time when short-lived (182)Hf was still present, we conclude that the metamorphosed sediments contain a component derived from meteorites.     

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.     

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.     

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.     

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.