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The “greenhouse” climates of the Paleocene and Eocene have formed the focus for many proxy and modelling studies in recent decades, as they are the closest geological analogues for our future warme...

Microcrystalline calcite (micrite) dominates the sedimentary record of the aftermath of the Cretaceous–Paleogene (K–Pg) impact at 31 sites globally, with records ranging from the deep ocean to the Chicxulub impact crater, over intervals ranging from a few centimeters to more than seventeen meters. This micrite-rich layer provides important information about the chemistry and biology of the oceans after the impact. Detailed high-resolution scanning electron microscopy demonstrates that the layer contains abundant calcite crystals in the micron size range with a variety of forms. Crystals are often constructed of delicate, oriented agglomerates of sub-micrometer mesocrystals indicative of rapid precipitation. We compare the form of crystals with natural and experimental calcite to shed light on their origin. Close to the crater, a significant part of the micrite may derive from the initial backreaction of CaO vaporized during impact. In more distal sites, simple interlocking rhombohedral crystals resemble calcite precipitated from solution. Globally, we found unique calcite crystals associated with fossilized extracellular materials that strikingly resemble calcite precipitated by various types of bacteria in natural and laboratory settings. The micrite-rich layer contains abundant bacterial and eukaryotic algal biomarkers and most likely represents global microbial blooms initiated within millennia of the K–Pg mass extinction. Cyanobacteria and non-haptophyte microalgae likely proliferated as dominant primary producers in cold immediate post-impact environments. As surface-water saturation state rose over the following millennia due to the loss of eukaryotic carbonate producers and continuing river input of alkalinity, “whitings” induced by cyanobacteria replaced calcareous nannoplankton as major carbonate producers. We postulate that the blooms grew in supersaturated surface waters as evidenced by crystals that resemble calcite precipitates from solution. The microbial biomass may have served as a food source enabling survival of a portion of the marine biota, ultimately including life on the deep seafloor. Although the dominance of cyanobacterial and algal photosynthesis would have weakened the biological pump, it still would have removed sufficient nutrients from surface waters thus conditioning the ocean for the recovery of biota at higher trophic levels.

The ratio of boron to calcium (B/Ca) in marine biogenic carbonates has been proposed as a proxy for properties of seawater carbonate chemistry. Applying this proxy to planktic foraminifera residing in the surface seawater largely in equilibrium with the atmosphere may provide a valuable handle on past atmospheric CO 2 concentrations. However, precise controls on B/Ca in planktic foraminifera remain enigmatic because it has been shown to depend on multiple physicochemical seawater properties. To help establish a firm inorganic basis for interpreting the B/Ca records, we examined the effect of a suite of chemical parameters ([Ca 2+ ], pH, [DIC], salinity and [PO 4 3− ]) on B/Ca in inorganic calcite precipitated in artificial seawater. These parameters were primarily varied individually while keeping all others constant, but we also tested the influence of pH and [DIC] at a constant calcite precipitation rate ( R ) by concurrent [Ca 2+ ] adjustments. In the simple [Ca 2+ ], pH and [DIC] experiments, both R and B/Ca increased with these parameters. In the pH–[Ca 2+ ] and [DIC]–[Ca 2+ ] experiments at constant R , on the other hand, B/Ca was invariant at different pH and decreased with [DIC], respectively. These patterns agree with the behavior of solution [B Total /DIC] ratio such that, at a fixed [B Total ], it is independent of pH but decreases with [DIC]. Based on these results, R and [B Total /DIC] ratio appear to be the primary controls on B/Ca in inorganic calcite, suggesting that both B(OH) 4 − and B(OH) 3 are possibly involved in B incorporation. Moreover, B/Ca modestly increased with salinity and [PO 4 3− ]. Inorganic calcite precipitated at higher R and in the presence of oxyanions such as SO 4 2− and PO 4 3− in growth solutions often undergoes surface roughening due to formation of crystallographic defects, vacancies and, occasionally, amorphous/hydrous CaCO 3 . These non-lattice sites may provide additional space for B, particularly B(OH) 3 . Consequently, besides the macroscopic influence of R and bulk solution chemistry, molecular-scale processes associated with calcite nucleation can be an important consideration for B incorporation, especially in complex ionic solutions. Lastly, the covariance of B/Ca with [DIC] and salinity observed here qualitatively agrees with those in planktic foraminifers. It follows that their impact on foraminiferal B/Ca is partly inorganically driven, which may explain why the effect is evident across different species.