The electrochemical behaviour of mild steel in aqueous solutions of sodium carbonate/sodium bicarbonate (600 ppm) has been investigated using potentiodynamic polarization. In the pre-passive region three well-defined peaks are observed associated to reduction peaks corresponding to Fe(II) and Fe(III) species. A transpassive anodic peak is also observed being attributed to Fe(VI) species showing, in sweep reversal experiments, an associated reduction peak and an increase in the peak associated to the reduction of Fe(III) species. The characterization of the transpassive peak will be subject of further publication.