Reaction pathway information of transition states and intermediate species is crucial for understanding the adsorption mechanism of pollutants at mineral-water interfaces. However, it has been difficult to obtain such information using existing experiments. Here, the activation barriers, transition states, intermediate species and surface complexes of arsenate adsorption on TiO2 surfaces were studied using DFT-based reaction pathway calculations. The results indicated that the bidentate binuclear (BB) adsorption structure was formed through a monodentate mononuclear (MM) metastable-equilibrium adsorption (MEA) state. A two-step adsorption mechanism was proposed on the basis of the detailed picture of bond breaking and bond formation during each reaction step. When the adjacent surface sites were occupied, the transform from MM mode to BB mode was greatly inhibited so that both MM and BB coexisted in the equilibrium adsorption sample. The BB complex was energetically more stable than the MM complex, and so, the adsorption irreversibility was fundamentally related to the ratio BB:MM in the final equilibrium state. This mechanism may also explain the initial concentration effect, where, for the given adsorption experiment of arsenate on TiO2 under the same thermodynamic conditions, both equilibrium constants and the BB:MM ratio in equilibrium adsorption samples changed with the reaction kinetics. (C) 2011 Elsevier Inc. All rights reserved.