Wastewater treatment plant (WWTP) mathematical models are based on the behavioural patterns of microorganisms involved in the treatment process. These microorganisms are assumed incapable of thinking or planning but simply act according to the capabilities afforded to them by their surrounding conditions – hence different microorganisms pre-dominate different WWTP zones according to how well the conditions suit them. When waste activated sludge (WAS) from biological nutrient removal (BNR) activated sludge (AS) systems, containing phosphorus-accumulating organisms (PAOs), is fed to an anaerobic digester, there is a release of high quantities of metals, phosphorus (P) and nitrogen (N). The manner in which we model the release of these metals and nutrients significantly affects the accuracy of predicted anaerobic digestion (AD) outcomes. Previous studies of PAOs show that in the anaerobic zone of the AS system, they can form energy-rich poly3-hydroxybutyrate (PHB) at the expense of their aerobically generated polyphosphate (PP). Thus, it is expected that the PAOs containing PP sent into an anaerobic digester with volatile fatty acids (VFAs) present, would utilize their PP reserves as they would in the anaerobic zone of an AS process ending up with formation and storage of some PHB. Ultimately, all the stored products of the PAO get released, since there is no alternating aerobic environment to cater for their growth. Since it has been established that the PP release in the AD occurs much faster than the PAO biomass hydrolysis rate, it is modelled as a separate process. Steps are presented in the development of this PP release mass-balanced stoichiometries that occur with AD of PAOs. By comparing outcomes from these proposed stoichiometries against measured experimental data, it is noticed that better predictions are obtained with acetate uptake for PHB formation than when modelling the AD PP release to occur with PAO death and hydrolysis.