Modeling the impacts of diagenesis on carbonate paleoredox proxies

The geochemistry of the carbonate sedimentary record is invaluable for understanding the ancient seawater evolution of carbon and redox-sensitive elements. However, the application of carbonate geochemical paleoredox proxies can be limited by our ability to recognize records impacted by syn- and post-depositional diagenesis with pore fluids that have geochemical compositions which are distinct from the overlying seawater—resulting from variable redox conditions, fluid sources, and sediment- vs seawater-buffered conditions. We extend a numerical framework, established for the application of Ca isotopes, for recognizing sediment- vs fluid-buffered alterations during aragonite-to-calcite recrystallization for widely applied carbonate paleoredox proxies: iodine ratios (I/Ca), cerium anomaly (Ce/Ce*), and carbonate-associated Cr, U, and S isotopes. We model endmember reducing and oxidizing fluid diagenetic scenarios, as opposed to incorporating biogeochemical evolution of pore fluids within the model. The results reveal that early, fluid-buffered diagenesis of relatively unevolved seawater (“seawater-buffered”) represents the ideal scenario for preservation for all proxies, including C isotopes. Conversely, fluid-buffered alteration in pore fluids with redox conditions highly evolved from the overlying water column is likely to alter the primary carbonate geochemistry. Model calibration against records from the Bahamas Clino and Unda cores suggests each proxy is uniquely sensitive to a given style of diagenetic alteration, with Ce/Ce* the most robust and I/Ca ratios most sensitive to early diagenetic alteration. We recommend multiple strategies, including relationships with C, O, and Ca isotope data, that can be leveraged to identify the preservation of primary seawater geochemistry for a given proxy. Last, we compare the diagenetic model predictions with published records from the Permian/Triassic boundary to demonstrate how incorporating stratigraphic geochemical patterns alongside interpretation of diagenetic model results can support interpretation of secular seawater signals. To improve our understanding of the effects of diagenesis on carbonate paleoredox proxies, additional experimental constraints, field-based observations, and multi-proxy datasets are needed.