The evolution of Phanerozoic seawater – Isotope paleothermometry finds consensus on Early Paleozoic warmth and constant seawater δ18O

Abstract:

Evolution of metazoan life is closely linked to the Phanerozoic evolution of ocean temperatures and chemistry. Oxygen isotopic evidence for early Phanerozoic paleotemperatures has been equivocal, with decreasing δ¹⁸O values with age being interpreted as warmer early oceans, decreasing seawater δ¹⁸O with age, or increasing diagenetic alteration in older samples. Here we compare an updated compilation of oxygen isotope data for carbonate and phosphate fossils and microfossils (Grossman, 2012, Geol. Time Scale, Elsevier, 195-220) with a compilation of new and existing clumped isotope data. Importantly, these data are curated based on sample preservation with special consideration given to screening techniques, and tectonic and burial history. Burial history is critical in the preservation of carbonate clumped isotope temperatures in particular, which can undergo reordering in the solid state. We use a model derived for reordering kinetics (Henkes et al., 2014, Geochim. Cosmochim. Acta 139:362-382) to screen clumped isotope data for the effects of solid-state burial alteration. With minor but significant exceptions (Late Cretaceous, Early Triassic), average δ¹⁸O values (4 m.y. window, 2 m.y. steps) for post-Devonian brachiopods, belemnites, and foraminifera, representing tropical-subtropical surface ocean conditions, yield average isotopic temperatures below 30°C (assuming a seawater δ¹⁸O value [ -1‰ VSMOW] of an “ice-free” world). In contrast, Ordovician to Devonian data show sustained temperatures of 35-40°C. Likewise, isotopic paleotemperatures from conodont apatite, known to be resistant to isotopic exchange, follow the same pattern. Clumped isotope data derived from Paleozoic brachiopod shells that experienced minimal burial (< 100 °C) and <1% reordering according to the taxon-specific clumped isotope reordering model yield typical temperatures of 25-30°C for the Carboniferous, and 35-40°C for the Ordovician-Silurian. Inserting clumped temperatures and δ¹⁸O values into the oxygen isotopic paleotemperature equation yields a mean seawater δ¹⁸O of -0.7 ± 1.4‰ for the Phanerozoic. Collectively, these findings argue for extremely warm early Paleozoic oceans, and constant seawater δ¹⁸O throughout the last ~450 million years.