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The Mesoproterozoic Eon [1,600–1,000 million years ago (Ma)] is emerging as a key interval in Earth history, with a unique geochemical history that might have influenced the course of biological evolution on Earth. Indeed, although this time interval is rather poorly understood, recent chromium isotope results suggest that atmospheric oxygen levels were <0.1% of present levels, sufficiently lowto have inhibited the evolution of animal life. In contrast, using a different approach, we explore the distribution and enrichments of redox-sensitive trace metals in the 1,400 Ma sediments of Unit 3 of the Xiamaling Formation, North China Block. Patterns of trace metal enrichments reveal oxygenated bottom waters during deposition of the sediments, and biomarker results demonstrate the presence of green sulfur bacteria in the water column. Thus, we document an ancient oxygen minimum zone. We develop a simple, yet comprehensive, model of marine carbon−oxygen cycle dynamics to show that our geochemical results are consistent with atmospheric oxygen levels >4% of present-day levels. Therefore, in contrast to previous suggestions, we show that there was sufficient oxygen to fuel animal respiration long before the evolution of animals themselves.

The cycles of carbon and oxygen at the Earth surface are intimately linked, where the burial of organic carbon into sediments represents a source of oxygen to the surface environment. This coupling is typically quantified through the isotope records of organic and inorganic carbon. Yet, the late Neoproterozoic Eon, the time when animals first evolved, experienced wild isotope fluctuations which do not conform to our normal understanding of the carbon cycle and carbon-oxygen coupling. We interpret these fluctuations with a new carbon cycle model and demonstrate that all of the main features of the carbonate and organic carbon isotope record can be explained by the release of methane hydrates from an anoxic dissolved organic carbon-rich ocean into an atmosphere containing oxygen levels considerably less than today.

We describe a 1,400 million-year old (Ma) iron formation (IF) from the Xiamaling Formation of the North China Craton. We estimate this IF to have contained at least 520 gigatons of authigenic Fe, comparable in size to many IFs of the Paleoproterozoic Era (2,500–1,600 Ma). Therefore, substantial IFs formed in the time window between 1,800 and 800 Ma, where they are generally believed to have been absent. The Xiamaling IF is of exceptionally low thermal maturity, allowing the preservation of organic biomarkers and an unprecedented view of iron-cycle dynamics during IF emplacement. We identify tetramethyl aryl isoprenoid (TMAI) biomarkers linked to anoxygenic photosynthetic bacteria and thus phototrophic Fe oxidation. Although we cannot rule out other pathways of Fe oxidation, iron and organic matter likely deposited to the sediment in a ratio similar to that expected for anoxygenic photosynthesis. Fe reduction was likely a dominant and efficient pathway of organic matter mineralization, as indicated by organic matter maturation by Rock Eval pyrolysis combined with carbon isotope analyses: Indeed, Fe reduction was seemingly as efficient as oxic respiration. Overall, this Mesoproterozoic-aged IF shows many similarities to Archean-aged (>2,500 Ma) banded IFs (BIFs), but with an exceptional state of preservation, allowing an unprecedented exploration of Fe-cycle dynamics in IF deposition.

Fluctuating climate is a hallmark of Earth. As one transcends deep into Earth time, however, both the evidence for and the causes of climate change become difficult to establish. We report geochemical and sedimentological evidence for repeated, short-term climate fluctuations from the exceptionally well-preserved ∼1.4-billion-year-old Xiamaling Formation of the North China Craton. We observe two patterns of climate fluctuations: On long time scales, over what amounts to tens of millions of years, sediments of the Xiamaling Formation record changes in geochemistry consistent with long-term changes in the location of the Xiamaling relative to the position of the Intertropical Convergence Zone. On shorter time scales, and within a precisely calibrated stratigraphic framework, cyclicity in sediment geochemical dynamics is consistent with orbital control. In particular, sediment geochemical fluctuations reflect what appear to be orbitally forced changes in wind patterns and ocean circulation as they influenced rates of organic carbon flux, trace metal accumulation, and the source of detrital particles to the sediment. Significance There is a wealth of evidence pointing to dramatic short-term climate change on Earth over the last few million years. Much of this climate change is driven by variations of Earth’s orbit around the Sun with characteristic frequencies known as Milankovitch cycles. Robust evidence for orbitally driven climate change, however, becomes rare as one descends deep into Earth time. We studied an exceptional record of climate change as recorded in 1.4-billion-year-old marine sediments from North China. This record documents regular changes in subtropical/tropical Hadley Cell dynamics. These changes in dynamics controlled wind strength, rainfall, and ocean circulation, translated into cyclic variations in sediment geochemistry, much like the orbital control on climate today and in the recent past.

The early Eocene (c. 56 - 48 million years ago) experienced some of the highest global temperatures in Earth’s history since the Mesozoic, with no polar ice. Reports of contradictory ice-rafted erratics and cold water glendonites in the higher latitudes have been largely dismissed due to ambiguity of the significance of these purported cold-climate indicators. Here we apply clumped isotope paleothermometry to a traditionally qualitative abiotic proxy, glendonite calcite, to generate quantitative temperature estimates for northern mid-latitude bottom waters. Our data show that the glendonites of the Danish Basin formed in waters below 5 °C, at water depths of <300 m. Such near-freezing temperatures have not previously been reconstructed from proxy data for anywhere on the early Eocene Earth, and these data therefore suggest that regionalised cool episodes punctuated the background warmth of the early Eocene, likely linked to eruptive phases of the North Atlantic Igneous Province.

After the evolution of oxygen-producing cyanobacteria at some time before 2.7 billion years ago, oxygen production on Earth is thought to have depended on the availability of nutrients in the oceans, such as phosphorus (in the form of orthophosphate). In the modern oceans, a significant removal pathway for phosphorus occurs by way of its adsorption onto iron oxide deposits. Such deposits were thought to be more abundant in the past when, under low sulphate conditions, the formation of large amounts of iron oxides resulted in the deposition of banded iron formations. Under these circumstances, phosphorus removal by iron oxide adsorption could have been enhanced. Here we analyse the phosphorus and iron content of banded iron formations to show that ocean orthophosphate concentrations from 3.2 to 1.9 billion years ago (during the Archaean and early Proterozoic eras) were probably only approximately 10-25% of present-day concentrations. We suggest therefore that low phosphorus availability should have significantly reduced rates of photosynthesis and carbon burial, thereby reducing the long-term oxygen production on the early Earth--as previously speculated--and contributing to the low concentrations of atmospheric oxygen during the late Archaean and early Proterozoic.

In the Jurassic period, the Early Toarcian oceanic anoxic event (about 183 million years ago) is associated with exceptionally high rates of organic-carbon burial, high palaeotemperatures and significant mass extinction 1 , 2 , 3 , 4 . Heavy carbon-isotope compositions in rocks and fossils of this age have been linked to the global burial of organic carbon, which is isotopically light. In contrast, examples of light carbon-isotope values from marine organic matter of Early Toarcian age have been explained principally in terms of localized upwelling of bottom water enriched in 12 C versus 13 C (refs 1 , 2 , 5 , 6 ). Here, however, we report carbon-isotope analyses of fossil wood which demonstrate that isotopically light carbon dominated all the upper oceanic, biospheric and atmospheric carbon reservoirs, and that this occurred despite the enhanced burial of organic carbon. We propose that—as has been suggested for the Late Palaeocene thermal maximum, some 55 million years ago 7 —the observed patterns were produced by voluminous and extremely rapid release of methane from gas hydrate contained in marine continental-margin sediments.

Oxygen concentration defines the chemical structure of Earth’s ecosystems while it also fuels the metabolism of aerobic organisms. As different aerobes have different oxygen requirements, the evolution of oxygen levels through time has likely impacted both environmental chemistry and the history of life. Understanding the relationship between atmospheric oxygen levels, the chemical environment, and life, however, is hampered by uncertainties in the history of oxygen levels. We report over 5,700 Raman analyses of organic matter from nine geological formations spanning in time from 742 to 1,729 Ma. We find that organic matter was effectively oxidized during weathering and little was recycled into marine sediments. Indeed, during this time interval, organic matter was as efficiently oxidized during weathering as it is now. From these observations, we constrain minimum atmospheric oxygen levels to between 2 to 24% of present levels from the late Paleoproterozoic Era into the Neoproterozoic Era. Indeed, our results reveal that eukaryote evolution, including early animal evolution, was not likely hindered by oxygen through this time interval. Our results also show that due to efficient organic recycling duringweathering, carbon cycle dynamics can be assessed directly from the sediment carbon record.

The cool of the Sun The faint early or 'young' Sun paradox, raised by Carl Sagan and George Mullen in 1972, points out that solar luminosity during the Archaean was about 70% of today's, so it would — the theory goes — have been too cold for liquid oceans to survive on Earth. Yet the geological record shows that liquid water was present. This is usually explained as the consequence of a greenhouse effect due to a high concentration of atmospheric carbon dioxide and/or methane. Minik Rosing et al . suggest that there is no need to invoke greenhouse warming — and no climate paradox. They demonstrate that the mineralogy of Archaean sediments is inconsistent with high greenhouse gas concentrations and the metabolic constraints of the methanogens of the time. They hypothesize that the low albedo of the early Earth, with little in the way of continents, and a preponderance of dark heat-absorbing ocean, together with a lack of biologically induced cloud condensation nuclei, were sufficient to maintain temperatures above freezing. It has been inferred that, during the Archaean eon, there must have been a high concentration of atmospheric CO 2 and/or CH 4 , causing a greenhouse effect that would have compensated for the lower solar luminosity at the time and allowed liquid water to be stable in the hydrosphere. Here it is shown, however, that the mineralogy of Archaean sediments is inconsistent with such high concentrations of greenhouse gases. Instead it is proposed that a lower albedo on the Earth helped to moderate surface temperature. Environmental niches in which life first emerged and later evolved on the Earth have undergone dramatic changes in response to evolving tectonic/geochemical cycles and to biologic interventions 1 , 2 , 3 , as well as increases in the Sun’s luminosity of about 25 to 30 per cent over the Earth’s history 4 . It has been inferred that the greenhouse effect of atmospheric CO 2 and/or CH 4 compensated for the lower solar luminosity and dictated an Archaean climate in which liquid water was stable in the hydrosphere 5 , 6 , 7 , 8 . Here we demonstrate, however, that the mineralogy of Archaean sediments, particularly the ubiquitous presence of mixed-valence Fe( II – III ) oxides (magnetite) in banded iron formations 9 is inconsistent with such high concentrations of greenhouse gases and the metabolic constraints of extant methanogens. Prompted by this, and the absence of geologic evidence for very high greenhouse-gas concentrations 10 , 11 , 12 , 13 , we hypothesize that a lower albedo on the Earth, owing to considerably less continental area and to the lack of biologically induced cloud condensation nuclei 14 , made an important contribution to moderating surface temperature in the Archaean eon. Our model calculations suggest that the lower albedo of the early Earth provided environmental conditions above the freezing point of water, thus alleviating the need for extreme greenhouse-gas concentrations to satisfy the faint early Sun paradox.