Reconstruction of Phanerozoic climate using carbonate clumped isotopes and implications for the oxygen isotopic composition of seawater

The oxygen isotope ratio ¹⁸O/¹⁶O (expressed as a δ¹⁸O_VSMOW value) in marine sedimentary rocks has increased by ~8‰ from the early Paleozoic to modern times. Interpretation of this trend is hindered by ambiguities in the temperature of formation of the carbonate, the δ¹⁸O_seawater, and the effects of postdepositional diagenesis. Carbonate clumped isotope measurements, a temperature proxy, offer constraints on this problem. This thermometer is thermodynamically controlled in cases where carbonate achieves an equilibrium internal distribution of isotopes and is independent of the δ¹⁸O of the water from which the carbonate grew; therefore, it has a relatively rigorous chemical-physics foundation and can be applied to settings where the δ¹⁸O of the water is not known. We apply this technique to an exceptionally well-preserved Ordovician carbonate record from the Baltic Basin and present a framework for interpreting clumped isotope results and for reconstructing past δ¹⁸O_seawater. We find that the seawater in the Ordovician had lower δ¹⁸O_seawater values than previously estimated, highlighting the need to reassess climate records based on oxygen-isotopes, particularly where interpretations are based on assumptions regarding either the δ¹⁸O_seawater or the temperature of deposition or diagenesis. We argue that an increase in δ¹⁸O_seawater contributed to the long-term rise in the δ¹⁸O of marine sedimentary rocks since the early Paleozoic. This rise might have been driven by a change in the proportion of high- versus low-temperature water-rock interaction in the earth's hydrosphere as a whole.