Constraints on ocean carbonate chemistry and p_CO2 in the Archaean and Palaeoproterozoic

One of the great problems in the history of Earth's climate is how to reconcile evidence for liquid water and habitable climates on early Earth with the Faint Young Sun predicted from stellar evolution models. Possible solutions include a wide range of atmospheric and oceanic chemistries, with large uncertainties in boundary conditions for the evolution and diversification of life and the role of the global carbon cycle in maintaining habitable climates. Increased atmospheric CO₂ is a common component of many solutions, but its connection to the carbon chemistry of the ocean remains unknown. Here we present calcium isotope data spanning the period from 2.7 to 1.9 billion years ago from evaporitic sedimentary carbonates that can test this relationship. These data, from the Tumbiana Formation, the Campbellrand Platform and the Pethei Group, exhibit limited variability. Such limited variability occurs in marine environments with a high ratio of calcium to carbonate alkalinity. We are therefore able to rule out soda ocean conditions during this period of Earth history. We further interpret this and existing data to provide empirical constraints for carbonate chemistry of the ancient oceans and for the role of CO₂ in compensating for the Faint Young Sun.