In this study, recycled Ni smelter slag has been used as a reactive medium for arsenic (As) removal from aqueous solutions. The results of the study showed that 10.16-11.43-cm long columns containing 451-550 g of slag operated for at least 65 days were able to remove 99-100 % As species from continuously flowing contaminated water at an initial As concentration of 10 mg/L. The removal capacities were found to be 1.039 to 1.054 mg As per g of slag. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy data also showed that electrostatic attraction and oxidation-reduction reactions between As species and mixed iron oxides present in the slag were the main mechanisms for the removal of arsenic from aqueous solutions. Theoretical multiplet analysis of XPS data revealed that the amount of goethite in the slag increased from 22 to 60 % during arsenic removal by adsorption and the percentage of magnetite decreased from 50 to 40 %. These changes indicate that redox-mediated reactions occurred as part of the As(V) removal process. Raman spectroscopy studies confirmed that, in addition to surface reactions, internal interactions between the slag and arsenic also occurred. The findings of the study suggest that recycled Ni smelter slag could be an effective low-cost reactive medium for a subsurface remediation system, such as a permeable reactive barrier. Recycling of waste material (slag) for the removal of another waste (arsenic) can significantly reduce the environmental footprint of metallurgical operations and hence contribute to sustainable development. Such recycling also decreases slag disposal costs and eliminates the need to purchase commercial reactive material or obtain expensive natural material for remediation purposes.