Fixation and Phase Transformation of Phosphate at Calcite Surfaces û Implications for Eutrophic Lake Restoration

Eutrophication of water bodies is one of the most severe environmental problems worldwide. It is well known that the availability of phosphate, as the limiting nutrient, is crucial for increased primary production and eutrophication. Calcite exhibits positive surface charge in most natural waters and can therefore be used for phosphate immobilisation. In this study, sorption experiments were performed in order to test different calcite materials regarding their suitability for use in restoration of eutrophic lakes. These short-term experiments were performed under different hydrochemical conditions (pH, SICC, initial dissolved P concentration) and with varying calcite properties (specific surface area and amount) in order to predict the long-term stability of the Ca-P-bonds. Peculiar shapes of isotherms that could not be explained only by adsorption processes were detected in the individual experiments. Depending on the residual P-concentration in solution, the isotherms can be divided into three sections indicating different processes responsible for the P-fixation on calcite surfaces. Adsorption prevails in equilibrium with lowest residual P-concentrations. The inflection of the isotherm at moderate residual P-concentrations suggests that precipitation and transformation of a Ca-P compound becomes dominant. This is supported by characteristic Ca/P-ratios for different Ca-P-compounds (b-tri- calcium-phosphate, octa-calcium-phosphate). On the new surface, phosphate ions again are fixed by adsorption. The observed transformation of P-bonding is crucial for sustainable phosphate immobilisation on calcite surfaces. While pure adsorption processes are reversible, the development of a thermodynamically stable Ca-P-phase, like hydroxylapatite, will lead to a lasting immobilisation of phosphate.