Temporal Evolution of Calcite Surface Dissolution Kinetics

This brief paper presents a rare dataset: a set of quantitative, topographic measurements of a dissolving calcite crystal over a relatively large and fixed field of view (~400 &mu:m2) and long total reaction time (&gt:6&nbsp:h). Using a vertical scanning interferometer and patented fluid flow cell, surface height maps of a dissolving calcite crystal were produced by periodically and repetitively removing reactant fluid, rapidly acquiring a height dataset, and returning the sample to a wetted, reacting state. These reaction-measurement cycles were accomplished without changing the crystal surface position relative to the instrument&rsquo:s optic axis, with an approximate frequency of one data acquisition per six minutes&rsquo: reaction (~10/h). In the standard fashion, computed differences in surface height over time yield a detailed velocity map of the retreating surface as a function of time. This dataset thus constitutes a near-continuous record of reaction, and can be used to both understand the relationship between changes in the overall dissolution rate of the surface and the morphology of the surface itself, particularly the relationship of (a) large, persistent features (e.g., etch pits related to screw dislocations: (b) small, short-lived features (e.g., so-called pancake pits probably related to point defects): (c) complex features that reflect organization on a large scale over a long period of time (i.e., coalescent &ldquo:super&rdquo: steps), to surface normal retreat and step wave formation. Although roughly similar in frequency of observation to an in situ atomic force microscopy (AFM) fluid cell, this vertical scanning interferometry (VSI) method reveals details of the interaction of surface features over a significantly larger scale, yielding insight into the role of various components in terms of their contribution to the cumulative dissolution rate as a function of space and time.