Calcium phosphate precipitation inside microbial granules cultivated in a granular sequenced batch reactor (GSBR) has been demonstrated to contribute to phosphorus removal during wastewater treatment. Whereas hydroxyapatite (HAP) is proven to accumulate in the granule, the main calcium phosphate precursors that form prior to HAP are here investigated. A separate batch reactor was used to distinguish reactions involving biological phosphate removal from physicochemical reactions involving phosphate precipitation in order to establish the kinetics and stoichiometry of calcium phosphate formation. Experiments and simulations with PHREEQC and AQUASIM software support the assumption that amorphous calcium phosphate (ACP) is the intermediary in HAP crystallization. The results provide the kinetic rate constants and thermodynamic constants of ACP. The formation of bioliths inside biological aggregates as well as the main parameters that drive their formations are discussed here. Finally, the influence of pH and calcium and phosphate concentrations in the influent was also assessed, in order to determine the contribution of precipitation in the different operating conditions. (C) 2012 Elsevier Ltd. All rights reserved.