Unveiling the secrets of diatom-mediated calcification: Implications for the biological pump

Siliceous diatoms are one of the most prominent actors in the oceans, and they account for approximately 40% of the primary production and particulate organic carbon export flux. It is believed that changes in carbon flux caused by variations in diatom distribution can lead to significant climate shifts. Although the fundamental pathways of diatom-driven carbon sequestration have long been established, there are no reports of CaCO₃ precipitation induced by marine diatom species. This manuscript introduces novel details regarding the enhancement of aragonite precipitation during photosynthesis in Skeletonema costatum in both artificial and natural seawater. Through direct measurements of cell surfaces via a pH microelectrode and zeta potential analyzer, it was determined that the diatom-mediated promotion of CaCO₃ precipitation is achieved through the creation of specific microenvironments with concentrated [CO₃²⁻] and [Ca²⁺] and/or the dehydrating effect of adsorbed Ca²⁺. Based on this mechanism, it is highly plausible that diatom-mediated calcification could occur in the oceans, an assertion that was supported by the significant deviation of total alkalinity (TA) from the conservative TA-salinity mixing line during a Skeletonema costatum bloom in the East China Sea and other similar occurrences. The newly discovered calcification pathway establishes a link between particulate inorganic and organic carbon flux and thus helps in the reassessment of marine carbon export fluxes and CO₂ sequestration efficiency. This discovery may have important ramifications for assessing marine carbon cycling and predicting the potential effects of future ocean acidification.