Tonian Carbonates Record Phosphate-Rich Shallow Seas

The early-middle Neoproterozoic is thought to have witnessed significant perturbations to marine P cycling, in turn facilitating the rise of eukaryote-dominated primary production. However, with few robust constraints on aqueous P concentrations, current understanding of Neoproterozoic P cycling is generally model-dependent. To provide new geochemical constraints, we combined microanalytical data sets with solid-state Nuclear Magnetic Resonance, synchrotron-based X-ray Absorption Near Edge Structure spectroscopy, and micro-X-ray Fluorescence imaging to characterize the speciation and distribution of P in Tonian shallow-water carbonate rocks. These data reflect shallow water phosphate concentrations 10-100x higher than modern systems, supporting the hypothesis that tectonically-driven influxes in P periodically initiated kinetically-controlled CaCO3 deposition, in turn destabilizing marine carbonate chemistry, climate, and nutrient inventories. Alongside these observations, a new compilation and statistical analysis of mudstone geochemistry data indicates that, in parallel, C-org and P burial increased across later Tonian continental margins until becoming decoupled at the close of the Tonian, implicating widespread N-limitation triggered by increasing atmospheric O-2.