Interactions between arsenic(V) and Fe3+ and Al3+ in aqueous solution were studied by potentiometry and, for Fe3+ system, by UV spectrophotometry too. Potentiometric measurements have evidenced the formation of FeAsO40, AlAsO40 and Al(AsO4)OH- species with formation constant values log beta = 17.77, 12.68 and 8.29, respectively, at I=0.1 mol L-1 and T=298.15 K. In order to applied speciation study to different kind of natural waters, the effect of the ionic strength on the thermodynamic parameters was analysed in the 0.1 <= 1 <= 0.7 mol L-1 range and modeled by a Debye-Huckel type equation. In addition, the formation enthalpy changes of the species were determined by direct calorimetric titrations, in order to define the effect of temperature on the strength of interactions. Examples of distribution of species were reported in different experimental conditions. Finally, the ability of arsenate "to sequester" Fe3+ and Al3+ cations was evaluated by pL(0.5) empiric parameter, that represents the ligand concentration required to sequester 50% of the metal cation present in traces. (C) 2017 Elsevier B.V. All rights reserved.