With the anticipated decrease in available anode raw materials, future anodes are expected to contain higher levels of impurities. Currently the implications of this are being investigated through evaluation of electrochemical performance of anodes and the environmental aspects through gas evolution studies. In this work, four experiments of aluminum smelting have been conducted with anodes of varying sulphur content. The aim of this work was to evaluate the speciation of sulphur in the off-gas. It was found that COS is the main sulphur species in the inert argon furnace atmosphere. The gas composition was further evaluated as a function of set anode voltages in potentiostatic mode. The significance levels of gas composition were evaluated through repeated experiments. As an FTIR multicomponent analyzer was used, less commonly discussed gaseous constituents such as CH4 and HCl were evaluated with respect to given impurity levels in the anode.