To predict the dynamic profiles in volatile fatty acids (VFAs) with pH and hydraulic retention time (HRT) during the startup of a 4-compartment ABR, a mathematical model was constructed by introducing pH and thermodynamic inhibition functions into the biochemical processes derived from the ADM1. The calibration of inhibition parameter for propionate uptake effectively improved the prediction accuracy of VFAs. The developed model could simulate the VFAs profiles very well no matter the observable change of pH or/and HRT. The simulation results indicated that both H-2-producing acetogenesis and methanogenesis in the ABR would be inhibited with a pH less than 4.61, and the propionate oxidation could be thermodynamically restricted even with a neutral pH. A decreased HRT would enhanced the acidogenesis and H-2-producing acetogenesis in the first 3 compartments, but no observable increase in effluent VFAs could be found due to the synchronously enhanced methanogenesis in the last compartment. (C) 2016 Elsevier Ltd. All rights reserved.