Records of Neogene seawater chemistry and diagenesis in deep-sea carbonate sediments and pore fluids

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10–20Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from −0.78‰ near the sediment–water interface to −0.15‰ at 778mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average δ²⁶Mg value of −4.72‰. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.