A kinetic pressure effect on calcite dissolution in seawater

This study provides laboratory data of calcite dissolution rate as a function of seawater undersaturation state (1 − Ω) under variable pressure. 13C-labeled calcite was dissolved in unlabeled seawater and the evolving δ13C composition of the fluid was monitored over time to evaluate the dissolution rate. Results show that dissolution rates are enhanced by a factor of 2-4 at 700 dbar compared to dissolution at the same Ω under ambient pressure (10 dbar). This dissolution rate enhancement under pressure applies over an Ω range of 0.65-1 between 10 dbar and 700 dbar. Above 700 dbar (up to 2500 dbar), dissolution rates become independent of pressure. The observed enhancement is well beyond the uncertainty associated with the thermodynamic properties of calcite under pressure (partial molar volume ΔV), and thus should be interpreted as a kinetic pressure effect on calcite dissolution. Dissolution at ambient pressure and higher pressures yield non-linear dissolution kinetics, the pressure effect does not significantly change the reaction order n in Rate = k(1 − Ω)n, which is shown to vary from 3.1 ± 0.3 to 3.8 ± 0.5 from 10 dbar to 700 dbar over Ω = 0.65-0.9. Furthermore, two different dissolution mechanisms are indicated by a discontinuity in the rate-undersaturation relationship, and seen at both ambient and higher pressures. The discontinuity, Ωcritical = 0.87 ± 0.05 and 0.90 ± 0.03 at 10 dbar and 1050 dbar respectively, are similar within error. The reaction order, n, at Ω > 0.9 is 0.47 ± 0.27 and 0.46 ± 0.15 at 10 dbar and 700 dbar respectively. This Ωcritical is considered to be the threshold between step retreat dissolution and defect-assisted dissolution. The kinetic enhancement of dissolution rates at higher pressures is related to a decrease in the interfacial energy barrier at dissolution sites. The impact of pressure on the calcite dissolution kinetics implies that sinking particles would dissolve at shallower depths than previously thought.