The Proterozoic aeon (2.5 to 0.54 billion years (Gyr) ago) marks the time between the largely anoxic world of the Archean (> 2.5 Gyr ago) and the dominantly oxic world of the Phanerozoic (< 0.54 Gyr ago). The course of ocean chemistry through the Proterozoic has traditionally been explained by progressive oxygenation of the deep ocean in response to an increase in atmospheric oxygen around 2.3 Gyr ago. This postulated rise in the oxygen content of the ocean is in turn thought to have led to the oxidation of dissolved iron, Fe(II), thus ending the deposition of banded iron formations (BIF) around 1.8 Gyr ago. An alternative interpretation suggests that the increasing atmospheric oxygen levels enhanced sulphide weathering on land and the flux of sulphate to the oceans. This increased rates of sulphate reduction, resulting in Fe(II) removal in the form of pyrite as the oceans became sulphidic. Here we investigate sediments from the approximately 1.8-Gyr-old Animikie group, Canada, which were deposited during the final stages of the main global period of BIF deposition. This allows us to evaluate the two competing hypotheses for the termination of BIF deposition. We use iron-sulphur-carbon (Fe-S-C) systematics to demonstrate continued ocean anoxia after the final global deposition of BIF and show that a transition to sulphidic bottom waters was ultimately responsible for the termination of BIF deposition. Sulphidic conditions may have persisted until a second major rise in oxygen between 0.8 to 0.58 Gyr ago, possibly reducing global rates of primary production and arresting the pace of algal evolution.

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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.

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The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today. However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆O) from sedimentary sulfates from the Sibley basin (Ontario, Canada) dated to about 1.4 billion years ago, which provide evidence for a less productive biosphere in the middle of the Proterozoic eon. We report what are, to our knowledge, the most-negative ∆O values (down to -0.88‰) observed in sulfates, except for those from the terminal Cryogenian period. This observation demonstrates that the mid-Proterozoic atmosphere was distinct from what persisted over approximately the past 0.5 billion years, directly reflecting a unique interplay among the atmospheric partial pressures of CO and O and the photosynthetic O flux at this time. Oxygenic gross primary productivity is stoichiometrically related to the photosynthetic O flux to the atmosphere. Under current estimates of mid-Proterozoic atmospheric partial pressure of CO (2-30 times that of pre-anthropogenic levels), our modelling indicates that gross primary productivity was between about 6% and 41% of pre-anthropogenic levels if atmospheric O was between 0.1-1% or 1-10% of pre-anthropogenic levels, respectively. When compared to estimates of Archaean and Phanerozoic primary production, these model solutions show that an increasingly more productive biosphere accompanied the broad secular pattern of increasing atmospheric O over geologic time.

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The Gunflint Formation, a Paleoproterozoic chemical–clastic sedimentary assemblage outcropping to the immediate northwest of Lake Superior, became famous in 1954 as containing the oldest fossil assemblage known at that time. Older microfossils have since been discovered, but the Gunflint procaryotes remain one of the most diverse Precambrian fossil communities. The finding of possible multicellular organisms in correlative lithic units in Michigan has recently added to the need for an exact age of the Formation. Zircons were extracted from rainout and storm reworked volcanoclastic beds in the upper portion of the Gunflint Formation. A euhedral zircon population has yielded a 1878.3 ± 1.3 million years BP U–Pb age, believed to be nearly synchronous with the depositional age. This not only provides a precise age for the community of organisms, but also strongly supports a back-arc extensional setting for the Animikie Basin, rather than a foreland trough.

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