Precessional pacing of early Proterozoic redox cycles

Regularly alternating reduction-oxidation (redox) patterns attributed to variations in the Earth's orbit and axis (Milankovitch cycles) are widely recorded in marine sediment successions of the Phanerozoic and attest to a dynamic history of biospheric oxygen in response to astronomically forced climate change. To date, however, such astronomical redox control remains elusive for much older, Precambrian intervals of the geological record that were characterized by a globally anoxic and iron-rich ocean, i.e., prior to Earth's atmospheric oxygenation (ca. 2.4–2.2 billion years ago). Here we report a detailed cyclostratigraphic and geochemical investigation of marine-sedimentary redox cycles identified in the ca. 2.46 billion-year-old Joffre Member of the Brockman Iron Formation, NW Australia, suggesting the imprint of Earth's climatic precession cycle. Around the base and top of regularly intercalated mudrock layers, we identify sharp enrichments in redox sensitive elements (Fe, S, Ca, P) that appear to represent chemical reaction fronts formed during nonsteady state diagenesis. Using a reactive transport model, we find that the formation of characteristic double S peaks required periods of increased organic matter deposition, coupled to strongly declining Fe2+ concentrations in the overlying water column. This combination, in turn, implies a periodic deepening of the iron chemocline due to enhanced oxygenic photosynthesis in marine surface waters, and is interpreted as the result of precession-induced changes in monsoonal intensity that drove variations in runoff and associated nutrient delivery. Our study results point to a dynamic redox evolution of Precambrian oceanic margin environments in response to Milankovitch forcing, and offer a temporal framework to investigate linkages between biological activity and the early build-up of oxygen in Earth's ocean-atmosphere system