Sulfide Immobilization: Investigating the Impact of a Protective Sulfide-Bearing Layer Formed by Siderite (FeCO₃)

Sulfate-rich wastewater poses ecological hazards to freshwater ecosystems, and sulfate is highly regulated in many Minnesota lakes. Biological sulfate reduction results in the reduction of sulfate to sulfide, and this process is used to remediate acid mine drainage. Theoretically, the aqueous sulfide can be immobilized into a solid-phase material and removed from the aqueous system. This study focuses on sulfide immobilization using iron-bearing waste minerals. Specifically, the extent of reaction of siderite (FeCO₃), an abundant ferrous mineral in some mining wastes, with sulfide was studied. Mildly acidic batch reactors containing powdered siderite were consecutively injected with a sodium sulfide solution. Solid reaction products were identified and characterized using powder X-ray diffraction, scanning and transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Mackinawite (FeS) appeared to be the most abundant product, with greigite (Fe₃S₄) also detected. Results reveal that the immobilization capacity of sulfide by siderite is limited by the concentration of the Fe²⁺(aq) presented in the system immediately before the initial sulfide exposure as the Fe²⁺(aq) levels are not replenished after sulfidation. These results improve our understanding of the sulfidation of siderite and provide insight to improve the viability of using siderite-containing mining waste rock in a sulfate remediation technology.