Dissolution and Precipitation Dynamics at Environmental Mineral Interfaces Imaged by In Situ Atomic Force Microscopy

, selenium, lead, cadmium, iron, chromium, and antimony. We detected the in situ replacement of these parent mineral phases by product phases, identified through a variety of analytical methods such as Raman spectroscopy, high-resolution transmission electron microscopy, and various X-ray techniques, as well as modeling by geochemical simulation using PHREEQC. As a consequence of the coupled processes, sequestration of toxic elements and hazardous species and inorganic and organic carbon, and limiting or promoting recovery of nutrients can be achieved at nano- and macroscopic scales.We also used in situ AFM to quantitatively measure the retreat rates of molecular steps and directly observe the morphology changes of dissolution etch pits on calcium phosphates in organic acid solutions present in most rhizosphere environments. By molecular modeling using density functional theory (DFT), we explain the origin of dissolution etch pit evolution through specific stereochemistry and molecular recognition and provide an energetic basis by calculating the binding energies of chemical functionalities on organic acids to direction-specific steps on mineral surfaces. In addition, we further quantified precipitation kinetics of calcium phosphates (Ca-P's) on typical mineral surfaces at the nanoscale in environmentally relevant solutions with various organic molecules, by measurements obtained from sequential images obtained by liquid-cell AFM. In situ dynamic force spectroscopy (DFS) was used to determine binding energies of single-molecules with different chemical functionalities found in natural organic matter at mineral-fluid interfaces. Quantifying molecular organo-mineral bonding or binding energies mechanistically explains phosphate precipitation and transformation. From DFS measurements, molecular-scale interactions of mineral-natural organic matter (DNA, proteins, and polysaccharides) associations were determined. With this powerful tool, single-molecule determinations of polysaccharide-amorphous iron oxide or hematite interactions provided the mechanistic origin of the phase- or facet-dependent adsorption. These systematic investigations and findings significantly contribute to a more quantitative prediction of the fate of nutrients and contaminants, chemical element cycling, and potential geological carbon capture and nuclear waste storage in aqueous environments.