Growth kinetics of step edges on celestite (001) 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 (001) surface have been measured as a function of temperature (23-45 degrees 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 [010]-aligned step edges, which are polar, and step edges vicinal to < 120 >, which are non-polar. [010] 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). (C) 2015 Elsevier Ltd. All rights reserved.