Growth kinetics of step edges on celestite (0 0 1) surfaces as a function of temperature, saturation state, ionic strength, and aqueous strontium:sulfate ratio: An in-situ atomic force microscopy study

Step velocities on the celestite (0 0 1) surface have been measured as a function of temperature (23–45 °C), saturation state (S = 1.1–2.2), ionic strength (I = 0.01, 0.06, and 0.1 M), and aqueous strontium:sulfate ratio (r = 0.01–100) using atomic force microscopy (AFM). Celestite growth hillocks were flanked by [0 1 0]-aligned step edges, which are polar, and step edges vicinal to 〈1 2 0〉, which are non-polar. [0 1 0] step velocities increased with temperature and saturation state, however step velocities did not vary significantly with ionic strength. Step velocities were non-linear with saturation state, suggesting a change in mechanism at high S as compared with low S. At constant S, the step velocities were maximized at r = 1 and decreased significantly at extreme r, demonstrating the governing role of solute stoichiometry. We successfully fit the step velocity data as a function of r using the Stack and Grantham (2010) nucleation and propagation model. Based on the results as a function of ionic strength and r, the mechanism at low S is likely ion-by-ion attachment to the step with an activation energy of 75 (±10) kJ mol⁻¹. At high S the mechanism is a combination of the one at low S and possibly attachment of a neutral species such as an ion pair with an activation energy of 43 (±9) kJ mol⁻¹.