Towards an understanding of the Ca isotopic signal related to ocean acidification and alkalinity overshoots in the rock record

In this contribution, we explore the idea that the Ca isotope proxy has utility as an indicator of carbonate authigenesis (i.e., post-depositional precipitation of CaCO₃ within the sedimentary package). Given the strong contrast in isotopic fractionation factor between the formational and diagenetic environments, Ca isotopes have the potential to fingerprint carbonate authigenesis when it occurs close to the seawater-sediment interface. We demonstrate that Ca isotopes are particularly applicable to exploring ocean acidification events, and potentially ocean anoxic events, and focus our attention on ocean acidification related to the Paleocene-Eocene Thermal Maximum (PETM). We present three scenarios that vary in the magnitude and duration of the carbon fluxes that are simulated using an Earth System model of intermediate complexity (cGENIE), and we use the cGENIE output to constrain the upper boundary conditions of 1-D reactive transport models of authigenesis and recrystallization in the sedimentary section. Along with simple mixing calculations, the models inform our exploration of the hypothesis that authigenic carbonate induced by a saturation state overshoot during the PETM explains recently published Ca isotope records, and perhaps bulk carbonate records over Ocean Anoxic Event (OAE) 2. Our simulations suggest that fractionation factor variability does not explain the PETM δ⁴⁴Ca records, and we propose a δ⁴⁴Ca-CaCO₃ space framework to assist with the elucidation of authigenic additions over time scales that are short relative to the residence time of Ca in the ocean (~1 Ma). Ultimately, we find that the ‘authigenic zone’ generated in the sedimentary column may be influenced by alkalinity overshoots or redox state; the CaCO₃ produced in this zone can overprint temporal signals with depth-dependent signals that reflect lithology and sedimentation rate and need not be spatially uniform, even when driven by a global event. Ultimately, we demonstrate the utility of Ca isotopes for exploring short time scale climatic events and a quantitative framework to guide interpretations.