Vanishing coccolith vital effects with alleviated carbon limitation

Abstract. By recreating a range of geologically relevant concentrations of dissolved inorganic carbon (DIC) in the laboratory, we demonstrate that the magnitude of the vital effects in both carbon and oxygen isotopes of coccolith calcite of multiple species relates to ambient DIC concentration. Under high DIC levels, all the examined coccoliths exhibit significantly reduced isotopic offsets from inorganic calcite compared to the substantial vital effects expressed at low (preindustrial and present-day) DIC concentrations. The supply of carbon to the cell exerts a primary control on biological fractionation in coccolith calcite via the modulation of coccolithophore growth rate, cell size and carbon utilisation by photosynthesis and calcification, altogether accounting for the observed interspecific differences between coccolith species. These laboratory observations support the recent hypothesis from field observations that the appearance of interspecific vital effect in coccolithophores coincides with the long-term Neogene decline of atmospheric CO₂ concentrations and bring further valuable constraints by demonstrating a convergence of all examined species towards inorganic values at high pCO₂ regimes. This study provides palaeoceanographers with a biogeochemical framework that can be utilised to further develop the use of calcareous nannofossils in palaeoceanography to derive sea surface temperature and pCO₂ levels, especially during periods of relatively elevated pCO₂ concentrations, as they prevailed during most of the Meso-Cenozoic.