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Copper slag, which contains Fe-rich fayalite (Fe2SiO4), is a valuable solid waste that warrants further research in order to recover iron. Calcium oxide (CaO) can significantly enhance iron recovery from copper slag; however, the associated mechanism has not yet been explored. In this study, we investigated the interaction between CaO and Fe2SiO4 to obtain detailed understanding of the role of CaO in enhancing iron recovery. The presence of CaO was found to accelerate the decomposition of Fe2SiO4 via an ion-exchange-like process. Specif