Transient crystallisation of rare earth carbonates during the hydrothermal oxidation of siderite

Abstract

The researchers investigated the interaction between multi-component rare earth element-bearing aqueous solutions and siderite grains under hydrothermal conditions. Our study investigates the interaction between multi-component rare earth element (REE; La, Ce, Pr, Nd, Dy)-bearing aqueous solutions and siderite (FeCO₃) grains under hydrothermal conditions (50–205 °C). The results revealed a solution-mediated mineral replacement reaction that occurs via a multi-step crystallisation pathway involving the formation of iron oxides (goethite, α-FeO(OH), and hematite, Fe₂O₃), metastable REE-bearing minerals (kozoite, REE(CO₃)(OH), and bastnasite, REE(CO₃)(OH,F)), and cerianite (CeO₂). Siderite stability, dissolution, and subsequent mineral formation are temperature and pH-dependent. At low temperatures, REE carbonate formation is inhibited by a goethite coating, creating a partial equilibrium situation. Higher temperatures increase dissolution rates and enable kozoite and bastnasite formation. The redox behaviour of Fe and Ce combined with the temperature, and the availability of CO₃²⁻ govern this crystallisation sequence. Continued oxidation promotes decarbonation processes by acidifying the aqueous solution, dissolving all carbonates, and resulting in hematite and cerianite crystallisation as thermodynamically stable phases. Understanding iron carbonate, oxide and REE interactions can inform new resource targets and improve recovery and separation techniques.