Method Summary:Rocks were collected from either drill core or surface outcrop without obvious weathering. Exterior surfaces were removed. Samples were powdered in a tungsten carbide mill from chips that were picked to avoid veins. Major element concentrations were determined using either an ICP-MS (Agilent 7500ce Series, or Thermo Element2) or an ICP-AES (Iris Advantage) after a three-acid dissolution or a metaborate fusion, respectively. Accuracy and precision for major element analyses was based on duplicates of the geostandards IF-G, SDO-1, and BHVO-1, and estimated error is less than 5%. For Mo isotopes, powdered samples were digested with concentrated HNO 3 + HF and HNO 3 + HCl, and then the samples were evaporated and dissolved with 7 mol/L HCl.

It has been suggested that a decrease in atmospheric methane levels triggered the progressive rise of atmospheric oxygen, the so-called Great Oxidation Event, about 2.4 Gyr ago. Oxidative weathering of terrestrial sulphides, increased oceanic sulphate, and the ecological success of sulphate-reducing microorganisms over methanogens has been proposed as a possible cause for the methane collapse, but this explanation is difficult to reconcile with the rock record. Banded iron formations preserve a history of Precambrian oceanic elemental abundance and can provide insights into our understanding of early microbial life and its influence on the evolution of the Earth system. Here we report a decline in the molar nickel to iron ratio recorded in banded iron formations about 2.7 Gyr ago, which we attribute to a reduced flux of nickel to the oceans, a consequence of cooling upper-mantle temperatures and decreased eruption of nickel-rich ultramafic rocks at the time. We measured nickel partition coefficients between simulated Precambrian sea water and diverse iron hydroxides, and subsequently determined that dissolved nickel concentrations may have reached approximately 400 nM throughout much of the Archaean eon, but dropped below approximately 200 nM by 2.5 Gyr ago and to modern day values ( approximately 9 nM) by approximately 550 Myr ago. Nickel is a key metal cofactor in several enzymes of methanogens and we propose that its decline would have stifled their activity in the ancient oceans and disrupted the supply of biogenic methane. A decline in biogenic methane production therefore could have occurred before increasing environmental oxygenation and not necessarily be related to it. The enzymatic reliance of methanogens on a diminishing supply of volcanic nickel links mantle evolution to the redox state of the atmosphere.

The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

Complex animals first evolved during the Ediacaran period, between 635 and 542 million years ago, when the oceans were just becoming fully oxygenated. In situ fossils of the mobile forms of these animals are associated with microbial sedimentary structures [1][2][3] , and the animal's trace fossils generally were formed parallel to the surface of the seabed, at or below the sediment-water interface 4,5 . This evidence suggests the earliest mobile animals inhabited settings with high microbial populations, and may have mined microbially bound sediments for food resources [6][7][8] . Here we report the association of mobile animals-insect larvae, oligochaetes and burrowing shore crabs-with microbial mats in a modern hypersaline lagoon in Venezuela. The lagoon is characterized by low concentrations of dissolved O 2 and pervasive biomats dominated by oxygen-producing cyanobacteria, both analogous to conditions during the Ediacaran. We find that, during the day, O 2 levels in the biomats are four times higher than in the overlying water column. We therefore conclude that the animals harvest both food and O 2 from the biomats. In doing so, the animals produce horizontal burrows similar to those found in Ediacaran-aged rocks. We suggest that early mobile animals may have evolved in similar environments during the Ediacaran, effectively exploiting oases rich in O 2 that formed within low oxygen settings.Although it is hypothesized that the appearance of the earliest mobile animals (putatively bilaterians) was made possible by the increasing abundance of dissolved oxygen in oceanic waters, dissolved oxygen ∼600 Myr was probably spatially variable and low overall, ranging between 10 and 18% of today's levels 9,10 . To most modern animals, persistently low oxygen concentrations are lethal-suggesting either that the first bilaterians were metabolically different from their modern counterparts, or that they exploited heretofore unrecognized sources of oxygen in the Ediacaran seas. Is it possible that oases of high oxygen concentration were present well before the Ediacaran and that they persisted in Ediacaran shallow marine environments, where photosynthetic biomats produced copious amounts of oxygen that diffused into the adjacent sediment and water column? Modern biomats-discussed belowcommonly have daytime oxygen concentrations that exceed atmospheric levels by several orders of magnitude 11 . This leads us to hypothesize that the first bilaterian animals did not need to evolve the ability to withstand low oxygen concentrations so much as to cope with spatiotemporal variability in oxygen availability.The trace-fossil record of bilaterian metazoans extends to the late Ediacaran about 555 Myr ago 12 (perhaps as early as 565 Myr; ref. 13)

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