ABSTRACT Arsenic is a common pollutant and impurity present in complex gold ores. In the pressure oxidation (POX) of refractory gold-bearing sulfides, a major environmental challenge is the treatment of the hazardous waste released from arsenic-bearing minerals during processing. While the bulk removal of arsenic from solution can occur during POX, the formation of stable arsenates relies on the operating conditions during POX and the subsequent curing stage. Herein, response surface methodology (RSM) and central composite design have been investigated as viable approaches for optimizing arsenic fixation during the curing of the POX product of arsenopyrite. Curing time (0–24 h) and temperature (60–120°C) were examined as the model variables for RSM optimization, and the performance was assessed via arsenic and iron precipitation, along with the change in free acid and sulfate concentrations. Experimental validation of the optimized model conditions demonstrated good agreement with the simulated outputs and provided a 10% increase in arsenic removal over the best model input. The formation of basic ferric arsenate sulfate and scorodite under these conditions was supported by RSM and confirmed via characterization. In the investigated system, the maximum arsenic removal occurs at a critical threshold temperature of 107°C, over which the scorodite formation decreases with temperature. Thermodynamic modeling revealed the preferable formation of soluble FeHAsO4 + complexes over scorodite above this threshold temperature, decreasing arsenic fixation at higher temperatures.