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 hypothesis that the establishment of a permanently oxygenated atmosphere at the Archaean-Proterozoic transition (approximately 2.5 billion years ago) occurred when oxygen-producing cyanobacteria evolved is contradicted by biomarker evidence for their presence in rocks 200 million years older. To sustain vanishingly low oxygen levels despite near-modern rates of oxygen production from approximately 2.7-2.5 billion years ago thus requires that oxygen sinks must have been much larger than they are now. Here we propose that the rise of atmospheric oxygen occurred because the predominant sink for oxygen in the Archaean era-enhanced submarine volcanism-was abruptly and permanently diminished during the Archaean-Proterozoic transition. Observations are consistent with the corollary that subaerial volcanism only became widespread after a major tectonic episode of continental stabilization at the beginning of the Proterozoic. Submarine volcanoes are more reducing than subaerial volcanoes, so a shift from predominantly submarine to a mix of subaerial and submarine volcanism more similar to that observed today would have reduced the overall sink for oxygen and led to the rise of atmospheric oxygen.

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.

The Early Palaeoproterozoic Brockman Supersequence comprises banded iron formation (BIF), bedded chert, limestone, mudrock, sandstone, breccia, tuffaceous mudstone, ashfall tuff and, in sections not reported here, basalt and rhyolite. Density current rhythms are preserved in sandstones, mudrocks, tuffaceous mudstones and limestones. Relics of similar rhythms in BIF imply that its precursor sediments were also deposited by density currents. Hemipelagic deposits are siliciclastic or mixed siliciclastic–volcaniclastic mudstones. Bedded chert, chert nodules and the chert matrix of BIF preserve evidence for formation by diagenetic replacement. For bedded chert (and chert nodules), silica replacement occurred before compaction close to or at the sediment–water interface, indicating that it is siliceous hardground. The chert matrix of BIF formed during compaction but before burial metamorphism. Original sediments were resedimented from two sources: (1) limestone, mudrock, sandstone, breccia and tuffaceous mudstone from a shelf; and (2) BIF from within the basin realm. Shelf sediments were resedimented to basin‐floor fans during third‐order lowstands. The precursor sediments to BIF are interpreted to have been granular hydrothermal muds, composed of iron‐rich smectite and particles of iron oxyhydroxide and siderite that were deposited on the flanks of submarine volcanoes and resedimented by density currents. Resedimentation occurred by either bottom currents or gravity‐driven turbidity currents, and the resulting sediment bodies may have been contourite drifts. The concept that BIF records high‐frequency alternating precipitation from ambient sea water of iron minerals and silica is negated by this study. Instead, it is postulated that the precursor sediments to BIF originated in much the same way as modern Red Sea hydrothermal iron oxide deposits, implying that at least the particles of iron oxyhydroxide originated from the oxidation of vent fluids by sea water. Several orders of cyclicity in basin filling establish a relationship between rising to high sea levels, episodic sea‐floor hydrothermal activity and BIF that is reminiscent of the link between eustacy and spreading‐ridge pulses.

[1] Situated south of the eastern Himalayan syntaxis at the western margin of the Shan-Thai terrane the highgrade Mogok metamorphic belt (MMB) in Myanmar occupies a key position in the tectonic evolution of Southeast Asia. The first sensitive high-resolution ion microprobe U-Pb in zircon geochronology for the MMB shows that strongly deformed granitic orthogneisses near Mandalay contain Jurassic ($170 Ma) zircons that have partly recrystallized during $43 Ma high-grade metamorphism. A hornblende syenite from Mandalay Hill also contains Jurassic zircons with evidence of Eocene metamorphic recrystallization rimmed by thin zones of 30.9 ± 0.7 Ma magmatic zircon. The relative abundance of Jurassic zircons in these rocks is consistent with suggestions that southern Eurasia had an Andean-type margin at that time. MidCretaceous to earliest Eocene (120 to 50 Ma) I-type granitoids in the MMB, Myeik Archipelago, and Western Myanmar confirm that prior to the collision of India, an up to 200 km wide magmatic belt extended along the Eurasian margin from Pakistan to Sumatra. Metamorphic overgrowths to zircons in the orthogneiss near Mandalay date a period of Eocene ($43 Ma) high-grade metamorphism possibly during crustal thickening related to the initial collision between India and Eurasia (at 65 to 55 Ma). This was followed by emplacement of syntectonic hornblende syenites and leucogranites between 35 and 23 Ma. Similar syntectonic syenites and leucogranites intruded the Ailao Shan-Red River shear belt in southern China and Vietnam during the Eocene-Oligocene to Miocene, and the Wang Chao and Three Pagodas faults in northern Thailand (that most likely link with the MMB) were also active at this time. The complex history of Eocene to early Miocene metamorphism, deformation, and magmatism in the MMB provides evidence that it may have played a key role in the network of deformation zones that accommodated strain during the northwards movement of India and resulting extrusion or rotation of Indochina.