Steel manufacturing byproducts were tested as a means of treating mine tailing leachate with a high As concentration. Byproduct materials can be placed in situ as permeable reactive barriers to control the subsurface release of leachate from tailing containment systems. The tested materials had various compositions of elemental Fe, Fe oxides, Ca-Fe oxides and Ca hydroxides typical of different steel manufacturing processes. Among these materials, evaporation cooler dust (ECD), oxygen gas sludge (OGS), basic oxygen furnace slag (BOFS) and to a lesser degree, electrostatic precipitator dust (EPD) effectively removed both As(V) and As(III) during batch experiments. ECD, OGS and BOFS reduced As concentrations to <0.5mg/l from 25mg/l As(V) or As(III) solution in 72 h, exhibiting higher removal capacities than zero-valent iron. High Ca concentrations and alkaline conditions (pH ca. 12) provided by the dissolution of Ca hydroxides may promote the formation of stable, sparingly soluble Ca-As compounds. When initial pH conditions were adjusted to 4, As reduction was enhanced, probably by adsorption onto iron oxides. The elution rate of retained As from OGS and ECD decreased with treatment time, and increasing the residence time in a permeable barrier strategy would be beneficial for the immobilization of As. When applied to real tailing leachate, ECD was found to be the most efficient barrier material to increase pH and to remove As and dissolved metals.