Adam V. Subhas

Catalysis and chemical mechanisms of calcite dissolution in seawater

Significance The experimental system described here provides constraints on the relative balance of gross dissolution and precipitation fluxes contributing to the observed net dissolution rate of calcite in seawater. We show that our dissolution rates fit well within a framework that accounts for the geometry of the dissolving mineral surface. We further show that carbonic anhydrase (CA) catalyzes calcite dissolution, which implicates the hydration of aqueous CO2 as a rate-limiting step for calcite dissolution in seawater. The presence of carbonic anhydrase in carbonate-rich environments such as coral reefs or sinking marine particles is poorly understood. However, our findings suggest that CA activity would significantly enhance the rate at which alkalinity is cycled between solids and seawater in these environments. Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric CO2 on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13C-labeled calcites in natural seawater. We show that the time-evolving enrichment of 𝜹13C in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution–precipitation shifts significantly toward a dissolution-dominated mechanism below about Ω= 0.7. Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of CO2 is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid–solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at Ω= 0.7, which we interpret as the onset of homogeneous etch pit nucleation.

Calibration of the B/Ca proxy in the planktic foraminifer Orbulina universa to Paleocene seawater conditions

The B/Ca ratio of planktic foraminiferal calcite, a proxy for the surface ocean carbonate system, displays large negative excursions during the Paleocene-Eocene Thermal Maximum (PETM, 55.9 Ma), consistent with rapid ocean acidification at that time. However, the B/Ca excursion measured at the PETM exceeds a magnitude that modern pH calibrations can explain. Numerous other controls on the proxy have been suggested, including foraminiferal growth rate and the total concentration of dissolved inorganic carbon (DIC). Here we present new calibrations for B/Ca versus the combined effects of pH and DIC in the symbiont-bearing planktic foraminifer Orbulina universa, grown in culture solutions with simulated Paleocene seawater elemental composition (high [Ca], low [Mg], and low total boron concentration ([B]_T). We also investigate the isolated effects of low seawater [B]_T, high [Ca], reduced symbiont photosynthetic activity, and average shell growth rate on O. universa B/Ca in order to further understand the proxy systematics and to determine other possible influences on the PETM records. We find that average shell growth rate does not appear to determine B/Ca in high calcite saturation experiments. In addition, our “Paleocene” calibration shows higher sensitivity than the modern calibration at low [B(OH)_4−]/DIC. Given a large DIC pulse at the PETM, this amplification of the B/Ca response can more fully explain the PETM B/Ca excursion. However, further calibrations with other foraminifer species are needed to determine the range of foraminifer species-specific proxy sensitivities under these conditions for quantitative reconstruction of large carbon cycle perturbations.