Variations in atmosphere oxygen and ocean sulfate concentrations through time are regarded as important controls on the cycles of sediment-hosted and volcanic-hosted ore deposits. However, estimates of atmosphere oxygen in the Proterozoic have been frustrated by the lack of a direct measurement method and conflicting evidence from various proposed geochemical proxies. Studies in the 1970s to 1990s suggested a relatively oxygenated atmosphere (> 3 wt% O₂) in the Proterozoic. However, since the late 1990s, new proxies and modelling have suggested very much lower levels of oxygen (< 0.02 wt% O₂). Focusing on redox-sensitive trace elements, here we combine a dataset of over 3000 LA-ICP-MS trace-element analyses on sedimentary pyrite, standardised against Berner’s Phanerozoic O₂ modelling and direct measurement of oxygen concentrations in fluid inclusions in sedimentary halite, to develop the first detailed estimate for atmosphere O₂ concentration and secular variation from 2200 Ma to the present. The estimates suggest dynamic cycles of atmosphere oxygen that increased in frequency through time. There were possibly three first-order cycles in the Proterozoic varying from 400 to 600 million years in length and a further five first-order cycles in the Phanerozoic from 60 to 120 million years in length. Our estimates of oxygen concentration are at odds with most previous estimates. We suggest, rather than very low atmosphere oxygen in the Proterozoic, the mean concentration was about 7 wt%, rising to a mean of about 10 wt% in the Phanerozoic, but with significant cyclic variation of up to a maximum concentration of possibly over 30 wt%. We observe that the proposed oxygen cycles correlate with biodiversity cycles and to the timing of major stratiform base-metal deposits in sedimentary basins. For example, minima in atmosphere oxygenation correlate with mass extinction events and stratiform Zn–Pb–Ag deposits, whereas maxima in oxygenation correlate with major evolutionary events, global periods of evaporite formation and the timing of stratiform copper deposits.

The period 1800 to 800 Ma (“Boring Billion”) is believed to mark a delay in the evolution of complex life, primarily due to low levels of oxygen in the atmosphere. Earlier studies highlight the remarkably flat C, Cr isotopes and low trace element trends during the so-called stasis, caused by prolonged nutrient, climatic, atmospheric and tectonic stability. In contrast, we suggest a first-order variability of bio-essential trace element availability in the oceans by combining systematic sampling of the Proterozoic rock record with sensitive geochemical analyses of marine pyrite by LA-ICP-MS technique. We also recall that several critical biological evolutionary events, such as the appearance of eukaryotes, origin of multicellularity & sexual reproduction, and the first major diversification of eukaryotes (crown group) occurred during this period. Therefore, it appears possible that the period of low nutrient trace elements (1800–1400 Ma) caused evolutionary pressures which became an essential trigger for promoting biological innovations in the eukaryotic domain. Later periods of stress-free conditions, with relatively high nutrient trace element concentration, facilitated diversification. We propose that the “Boring Billion” was a period of sequential stepwise evolution and diversification of complex eukaryotes, triggering evolutionary pathways that made possible the later rise of micro-metazoans and their macroscopic counterparts.