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Secondary iron oxides formed in acid mine drainage, such as schwertmannite, are scavengers for metal(loid)s in mining environments. Increasing the understanding of the geochemical transformations of these minerals, as well as knowing how metal(loid)s affect these transformations, is crucial to ultimately predict the fate of these trace elements in acidic mine drainage and to minimize the potential environmental risk. In this study, transformation experiments have been conducted with a schwertmannite-rich sediment collected from a mining area and with synthesized schwertmannite as a reference material. The transformation of schwertmannite into goethite was studied as a function of the presence of arsenic, pH value, and redox conditions. Arsenic delayed the mineral transformation from pseudo-stable amorphous phases to more stable crystalline forms, especially at higher arsenic loadings and more acidic pH. Experiments in the presence of Fe(II) and ascorbic acid have proven that both components promote the mineral transformation or reductive dissolution of schwertmannite under anoxic conditions. The presence of arsenic reduced the catalytic effect of Fe(II), stabilizing the schwertmannite particles. On the other hand, arsenic had no effect on the reductive dissolution at these conditions when ascorbic acid was used as a reducing agent.