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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.

Establishing when, and from where, carbon, nitrogen and water were delivered to Earth is a fundamental objective in understanding the origin of habitable planets such as Earth. Yet, volatile delivery to Earth remains controversial

Neodymium isotopes from fossil fish teeth and tectonic reconstructions show that the deep Tasmanian Gateway opened up about 33 million years ago and that the Antarctic Circumpolar Current arose 30 million years ago, when the gateway probably moved into the latitudes of the strong westerly winds. Ocean circulations were transformed during the Oligocene, when a series of tectonic movements reshaped the continents into a pattern that began to resemble what we see today. In particular the Drake Passage (between South America and Antarctica) and the Tasmanian Gateway (between Australia and Antarctica) opened and provided channels for the Antarctic Circumpolar Current. The sequence and timing of these events are uncertain. Here Howie Scher et al. use neodymium isotopes extracted from fossilized fish teeth as well as tectonic reconstructions to show that the deep Tasmanian Gateway opened up about 33 million years ago, and that the Antarctic Circumpolar Current arose 3 million years later, when the gateway probably moved into the latitudes of the strong westerly winds. Earth’s mightiest ocean current, the Antarctic Circumpolar Current (ACC), regulates the exchange of heat and carbon between the ocean and the atmosphere1, and influences vertical ocean structure, deep-water production2 and the global distribution of nutrients and chemical tracers3. The eastward-flowing ACC occupies a unique circumglobal pathway in the Southern Ocean that was enabled by the tectonic opening of key oceanic gateways during the break-up of Gondwana (for example, by the opening of the Tasmanian Gateway, which connects the Indian and Pacific oceans). Although the ACC is a key component of Earth’s present and past climate system1, the timing of the appearance of diagnostic features of the ACC (for example, low zonal gradients in water-mass tracer fields4,5,6,7) is poorly known and represents a fundamental gap in our understanding of Earth history. Here we show, using geophysically determined positions of continent–ocean boundaries8, that the deep Tasmanian Gateway opened 33.5 ± 1.5 million years ago (the errors indicate uncertainty in the boundary positions). Following this opening, sediments from Indian and Pacific cores recorded Pacific-type neodymium isotope ratios, revealing deep westward flow equivalent to the present-day Antarctic Slope Current. We observe onset of the ACC at around 30 million years ago, when Southern Ocean neodymium isotopes record a permanent shift to modern Indian–Atlantic ratios. Our reconstructions of ocean circulation show that massive reorganization and homogenization of Southern Ocean water masses coincided with migration of the northern margin of the Tasmanian Gateway into the mid-latitude westerly wind band, which we reconstruct at 64° S, near to the northern margin. Onset of the ACC about 30 million years ago coincided with major changes in global ocean circulation9 and probably contributed to the lower atmospheric carbon dioxide levels that appear after this time10.

Changes in environmental conditions at the Precambrian–Cambrian transition (around 542 million years ago) have been suggested as a possible explanation for the apparent rapid increase in abundance of multicellular organisms known as the 'Cambrian explosion'. The nature of the environmental changes is still a matter of debate, however. Wille et al. now report molybdenum isotope signatures of black shales from two stratigraphically correlated sample sets with a depositional age of about 542 million years. With the help of a box model of the oceanic molybdenum cycle, they find that intense upwelling of hydrogen sulphide-rich deep ocean water best explains the observed early Cambrian molybdenum isotope signal. This suggests that the early Cambrian animal radiation may have been triggered by a major change in ocean circulation, following a long period during which the ocean was stratified, with sulphidic deep water. This paper reports molybdenum isotope signatures of black shales from two stratigraphically correlated sample sets with a depositional age of around 542 million years. The findings suggest that the Early Cambrian animal radiation may have been triggered by a major change in ocean circulation, terminating a long period during which the Proterozoic ocean was stratified, with sulphidic deep water. Animal-like multicellular fossils appeared towards the end of the Precambrian, followed by a rapid increase in the abundance and diversity of fossils during the Early Cambrian period, an event also known as the ‘Cambrian explosion’1,2,3. Changes in the environmental conditions at the Precambrian/Cambrian transition (about 542 Myr ago) have been suggested as a possible explanation for this event, but are still a matter of debate1,2,3. Here we report molybdenum isotope signatures of black shales from two stratigraphically correlated sample sets with a depositional age of around 542 Myr. We find a transient molybdenum isotope signal immediately after the Precambrian/Cambrian transition. Using a box model of the oceanic molybdenum cycle, we find that intense upwelling of hydrogen sulphide-rich deep ocean water best explains the observed Early Cambrian molybdenum isotope signal. Our findings suggest that the Early Cambrian animal radiation may have been triggered by a major change in ocean circulation, terminating a long period during which the Proterozoic ocean was stratified, with sulphidic deep water.

The terrestrial sediment record indicates that the Earth's climate varied drastically in the Precambrian era (before 550 million years ago), ranging from surface temperatures similar to or higher than today's to global glaciation events. The most continuous record of sea surface temperatures of that time has been derived from variations in oxygen isotope ratios of cherts (siliceous sediments), but the long-term cooling of the oceans inferred from those data has been questioned because the oxygen isotope signature could have been reset through the exchange with hydrothermal fluids after deposition of the sediments. Here we show that the silicon isotopic composition of cherts more than 550 million years old shows systematic variations with age that support the earlier conclusion of long-term ocean cooling and exclude post-depositional exchange as the main source of the isotopic variations. In agreement with other lines of evidence, a model of the silicon cycle in the Precambrian era shows that the observed silicon isotope variations imply seawater temperature changes from about 70 degrees C 3,500 million years ago to about 20 degrees C 800 million years ago.

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 oölites 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.

The Earth's most severe glaciations are thought to have occurred about 600 million years ago, in the late Neoproterozoic era1,2. A puzzling feature of glacial deposits from this interval is that they are overlain by 1–5-m-thick ‘cap carbonates’ (particulate deep-water marine carbonate rocks) associated with a prominent negative carbon isotope excursion3,4,5,6,7,8. Cap carbonates have been controversially ascribed to the aftermath of almost complete shutdown of the ocean ecosystems for millions of years during such ice ages—the ‘snowball Earth’ hypothesis4,5. Conversely, it has also been suggested that these carbonate rocks were the result of destabilization of methane hydrates during deglaciation and concomitant flooding of continental shelves and interior basins3. The most compelling criticism of the latter ‘methane hydrate’ hypothesis has been the apparent lack of extreme isotopic variation in cap carbonates inferred locally to be associated with methane seeps. Here we report carbon isotopic and petrographic data from a Neoproterozoic postglacial cap carbonate in south China that provide direct evidence for methane-influenced processes during deglaciation. This evidence lends strong support to the hypothesis that methane hydrate destabilization contributed to the enigmatic cap carbonate deposition and strongly negative carbon isotopic anomalies following Neoproterozoic ice ages. This explanation requires less extreme environmental disturbance than that implied by the snowball Earth hypothesis4,5.

Many independent lines of evidence document a large increase in the Earth's surface oxidation state 2,400 to 2,200 million years ago1,2,3,4, and a second biospheric oxygenation 800 to 580 million years ago, just before large animals appear in the fossil record5,6. Such a two-staged oxidation implies a unique ocean chemistry for much of the Proterozoic eon, which would have been neither completely anoxic and iron-rich as hypothesized for Archaean seas, nor fully oxic as supposed for most of the Phanerozoic eon7. The redox chemistry of Proterozoic oceans has important implications for evolution8, but empirical constraints on competing environmental models are scarce. Here we present an analysis of the iron chemistry of shales deposited in the marine Roper Basin, Australia, between about 1,500 and 1,400 million years ago, which record deep-water anoxia beneath oxidized surface water. The sulphur isotopic compositions of pyrites in the shales show strong variations along a palaeodepth gradient, indicating low sulphate concentrations in mid-Proterozoic oceans. Our data help to integrate a growing body of evidence favouring a long-lived intermediate state of the oceans, generated by the early Proterozoic oxygen revolution and terminated by the environmental transformation late in the Proterozoic eon.

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.