Direct Imaging of Nanoscale Dissolution of Dicalcium Phosphate Dihydrate by an Organic Ligand: Concentration Matters

Unraveling the kinetics and mechanisms of sparingly soluble calcium orthophosphate (Ca–P) dissolution in the presence of organic acids at microscopic levels is important for an improved understanding in determining the effectiveness of organic acids present in most rhizosphere environments. Herein, we use in situ atomic force microscopy (AFM) coupled with a fluid reaction cell to image dissolution on the (010) face of brushite, CaHPO<sub>4</sub>·2H<sub>2</sub>O, in citrate-bearing solutions over a broad concentration range. We directly measure the dependence of molecular step retreat rate on citrate concentration at various pH values and ionic strengths, relevant to soil solution conditions. We find that low concentrations of citrate (10–100 μM) induced a reduction in step retreat rates along both the [1̅00]­Cc and [101̅]­Cc directions. However, at higher concentrations (exceeding 0.1 mM), this inhibitory effect was reversed with step retreat speeds increasing rapidly. These results demonstrate that the concentration-dependent modulation of nanoscale Ca–P phase dissolution by citrate may be applied to analyze the controversial role of organic acids in enhancing Ca–P mineral dissolution in a more complex rhizosphere environment. These in situ observations may contribute to resolving the previously unrecognized interactions of root exudates (low molecular weight organic acids) and sparingly soluble Ca–P minerals.