Cycling phosphorus on the Archean Earth: Part I. Continental weathering and riverine transport of phosphorus

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Phosphorus (P) is the key nutrient thought to limit primary productivity on geological timescales. Phosphate levels in Archean marine sediments are low, but quantification of the P cycle and how it changed through a billion years of recorded Archean history remain a challenge, hindering our understanding of the role played by P in biosphere/geosphere co-evolution on the early Earth.Here, we design kinetic and thermodynamic models to quantitatively assess one key component of the early P cycle – continental weathering – by considering the emergence and elevation of continents, as well as the evolution of climate, the atmosphere, and the absence of macroscopic vegetation during the Archean Eon. Our results suggest that the weathering rate of apatite, the major P-hosting mineral in the rocks, was at least five times higher in the Archean Eon than today, attributable to high levels of pCO2,g. Despite this, the weathering flux of P to the oceans was negligible in the early Archean Eon, increasing to a level comparable to or greater than the modern by the end of eon, a consequence of accelerating continental emergence. Furthermore, our thermodynamic calculations indicate high solubilities of primary and secondary P-hosting minerals in the acidic weathering fluids on land, linking to high Archean pCO2,g. Thus, weathering of P was both kinetically and thermodynamically favorable on the Archean Earth, and river water could transport high levels of dissolved P to the oceans, as also supported by the observed P-depletion in our new compilation of Archean paleosols. Lastly, we evaluated the relative rates of physical erosion and chemical weathering of silicates during the Archean Eon. The results suggest that continental weathering on the early and middle Archean Earth might have been transport-limited due to low erosion rates associated with limited subaerial emergence and low plateau elevations; by the late Archean, however, continental weathering would have transited to kinetically-limited state because of continental emergence, increased plateau elevation, and weakening weathering rates. Overall, our weathering calculations together with paleosol evidence indicate an increasing flux of bioavailable P to the oceans through time, associated with late Archean continental emergence, reaching levels comparable to or higher than modern values by the end of the eon. Increased P fluxes could have fueled increasing rates of primary production, including oxygenic photosynthesis, through time, facilitating the irreversible oxidation of the Earth’s atmosphere early in the Proterozoic Eon.