The partial pressure of oxygen in Earth's atmosphere has increased dramatically through time, and this increase is thought to have occurred in two rapid steps at both ends of the Proterozoic Eon (∼2.5-0.543 Ga). However, the trajectory and mechanisms of Earth's oxygenation are still poorly constrained, and little is known regarding attendant changes in ocean ventilation and seafloor redox. We have a particularly poor understanding of ocean chemistry during the mid-Proterozoic (∼1.8-0.8 Ga). Given the coupling between redoxsensitive trace element cycles and planktonic productivity, various models for mid-Proterozoic ocean chemistry imply different effects on the biogeochemical cycling of major and trace nutrients, with potential ecological constraints on emerging eukaryotic life. Here, we exploit the differing redox behavior of molybdenum and chromium to provide constraints on seafloor redox evolution by coupling a large database of sedimentary metal enrichments to a mass balance model that includes spatially variant metal burial rates. We find that the metal enrichment record implies a Proterozoic deep ocean characterized by pervasive anoxia relative to the Phanerozoic (at least ∼30-40% of modern seafloor area) but a relatively small extent of euxinic (anoxic and sulfidic) seafloor (less than ∼1-10% of modern seafloor area). Our model suggests that the oceanic Mo reservoir is extremely sensitive to perturbations in the extent of sulfidic seafloor and that the record of Mo and chromium enrichments through time is consistent with the possibility of a Mo-N colimited marine biosphere during many periods of Earth's history.paleoceanography | geobiology

We review recent observations and models concerning the dynamics of Cryogenian global glaciation and their biological consequences.

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Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages have yielded new, and potentially more direct, insights into secular changes in seawater composition -and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT3 sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies.

International audienceThe concept of the Great Oxidation Event (GOE), during which atmospheric oxygen rose precipitously and perhaps to near-modern levels around 2.4-2.1 billion years ago (Ga), has become entrenched in our views on secular atmospheric evolution. Multiple proxies confirm a permanent shift towards more oxygenated conditions at some time near the Archean-Proterozoic boundary. However, it remains unclear precisely when this transition occurred, due in part to the likely temporal variability in those early levels and different sensitivities of the proxies utilized to track atmospheric oxygen partial pressures. Here, we provide a new look at the timing and magnitude of early atmospheric oxygenation through the record of uranium (U) concentrations in iron formations (IF). Just as IF are important archives of the redox state of seawater, concentrations of redox-sensitive U in IF are faithful proxies for oxidative continental weathering and associated delivery of dissolved U to seawater. Our dataset suggests that there was an increase in U redox cycling and transport at ca. 2.47 Ga, just before the permanent loss of mass-independent sedimentary sulfur isotope anomalies traditionally used to define the onset of the GOE. Further, there is significant temporal variability in the IF U record that we propose reflects dynamic Precambrian redox conditions. We provide additional support for earlier suggestions that the GOE was a protracted event marked by vacillating oxygen levels

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