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Alkenones are long-chain ketones produced by phytoplankton of the order Isochrysidales. They are widely used in reconstructing past sea surface temperatures, benefiting from their ubiquitous occurrence in the Cenozoic ocean. Carbon isotope fractionation (εp) between alkenones and dissolved inorganic carbon may also be used as a proxy for past atmospheric pCO2 and has provided continuous pCO2 estimates back to ca. 45 Ma. Here, an extended occurrence of alkenones from ca. 130 Ma is reported. We characterize the molecular structure and distribution of these Mesozoic alkenones and evaluate their potential phylogenetic relationship with Cenozoic alkenones. Using δ13C values of the C37 methyl alkenone (C37:2Me), the first alkenone-based pCO2 estimates for the Mesozoic are derived. These estimates suggest elevated pCO2 with a range of 548−4090 ppm (908 ppm median) during the super-greenhouse climate of the Early Cretaceous, in agreement with phytane-based pCO2 reconstructions. Finally, insights into the identity of the Cretaceous coccolithophores that possibly synthesized alkenones are also offered. 

Changes in plate tectonics drove degassing of carbon dioxide and global temperatures over the past 20 million years. 

Abstract Ocean acidification due to anthropogenic CO₂emission reduces ocean pH and carbonate saturation, with the projection that marine calcifiers and associated ecosystems will be negatively affected in the future. On longer time scale, however, recent studies of deep‐sea carbonate sediments suggest significantly increased carbonate production and burial in the open ocean during the warm Middle Miocene. Here, we present new model simulations in comparison to published Miocene carbonate accumulation rates to show that global biogenic carbonate production in the pelagic environment was approximately doubled relative to present‐day values when elevated atmosphericpCO₂led to substantial global warming ∼13–15 million years ago. Our analysis also finds that although high carbonate production was associated with high dissolution in the deep‐sea, net pelagic carbonate burial was approximately 30%–45% higher than modern. At the steady state of the long‐term carbon cycle, this requires an equivalent increase in riverine carbonate alkalinity influx during the Middle Miocene, attributable to enhanced chemical weathering under a warmer climate. Elevated biogenic carbonate production resulted in a Miocene ocean that had carbon (dissolved inorganic carbon) and alkalinity (total alkalinity) inventories similar to modern values but was poorly buffered and less saturated in both the surface and the deep ocean relative to modern.