Reconstructing Neoproterozoic seawater chemistry from early diagenetic dolomite

The pairing of calcium and magnesium isotopes (δ44/40Ca, δ26Mg) has recently emerged as a useful tracer to understand the environmental information preserved in shallow-marine carbonates. Here, we applied a Ca and Mg isotopic framework, along with analyses of carbon and lithium isotopes, to late Tonian dolostones, to infer seawater chemistry across this critical interval of Earth history. We investigated the ca. 735 Ma Coppercap Formation in northwestern Canada, a unit that preserves large shifts in carbonate δ13C values that have been utilized in global correlations and have canonically been explained through large shifts in organic carbon burial. Under the backdrop of these δ13C shifts, we observed positive excursions in δ44/40Ca and δ7Li values that are mirrored by a negative excursion in δ26Mg values. We argue that this covariation is due to early diagenetic dolomitization of aragonite through interaction with contemporaneous seawater under a continuum of fluid- to sediment-buffered conditions. We then used this framework to show that Tonian seawater was likely characterized by a δ7Li value of ~13‰ (~18‰ lower than modern seawater), as a consequence of a different Li cycle than today. In contrast, δ13C values across our identified fluid-buffered interval are similar to modern seawater. These observations suggest that factors other than shifts in global seawater chemistry are likely responsible for such isotopic variation.