The Rare Earth Element Distribution in Marine Carbonates as a Potential Proxy for Seawater pH on Early Earth

Understanding the marine environment of early Earth is crucial for understanding the evolution of climate and early life. However, the master variable of Archean and Proterozoic seawater, the pH, is poorly constrained, and published ideas about the pH range encompass ~7 pH units from mildly acidic to hyperalkaline. To better infer ancient seawater pH, we examine the possibility of a seawater pH proxy using rare earth elements (REEs) in marine carbonates. The principle is based on increasing concentrations of heavy rare earth elements in solution relative to the light REEs with decreasing pH due to REE complexation and scavenging. We calibrated such an REE pH proxy using pH variability in modern seawater and tested the proxy with ~100 REE measurements from 13 separate carbonate formations. We compared our pH estimates derived from the REE proxy to published pH estimates of Cenozoic and Neoproterozoic seawater that use the established pH proxy of boron isotopes (δ 11 B). REE-pH estimates agree with the Cenozoic and the Ediacaran δ 11 B-pH proxy based on the type of carbonate and boron isotopic composition at corresponding times. The uncertainty in our REE-pH proxy can probably be explained by model assumptions, noise from freshwater influence, siliciclastic input, and diagenesis. This proof-of-concept study demonstrates that the REE-pH method provides pH estimates comparable to boron isotope pH estimates within uncertainties, which potentially could constrain changes in Precambrian seawater pH to better understand the coevolution of life and early Earth’s environment.