Microscopic effects of carbonate, manganese, and strontium ions on calcite dissolution

Aqueous dissolution of the (10 (1) over bar4) surface of calcite was observed at pH near 9 by using an atomic Force microscope equipped with a fluid cell. The influences of carbonate (CO32-), strontium (Sr2+), and manganese (Mn2+) ion concentrations on the rates of step motion were measured. Carbonate ions were shown to have a step-specific effect on calcite dissolution. At low levels (<1 <mu>M) of CO32-, the retreat rate of the more structurally open [(4) over bar 41](+) steps was faster than the retreat rate of the structurally confined [(4) over bar 41]_ steps, leading to anisotropic dissolution. Increasing the CO32- level to as high as 900 muM decreased the rate of retreat of both steps. but the [(4) over bar 41](+) step was slowed to a much greater extent changing the degree of dissolution anisotropy. This decrease in step velocity at high CO32- levels was attributed to a corresponding increase in the back reaction (i.e., precipitation) as the solution approached saturation with respect to calcite. Strontium cations were also shown to have a step-specific effect on calcite dissolution similar to that of CO32-. Manganese cations, on the other hand, slowed the rate of retreat of the [(4) over bar 41] step to a greater extent than Sr2+. The influence of impurity metal sorption on dissolution is examined in terms of sorption at kinks and the dissolution behavior is explained in terms of a terrace-ledge-kink site-blocking model. Evidence is given to support the hypothesis that ion-pairs formed in solution are the primary growth units for calcite. Copyright (C) 2000 Elsevier Science Ltd.