Investigation of Cd(II) sorption by mackinawite (FeS) under anoxic conditions

Mackinawite (FeS) was investigated for cadmium ion (Cd(II)) sorption under anoxic conditions. At the surface loading of Cd(II) (i.e., [Cd(II)] 0 /[FeS] 0 ) ≤ 5 mmol/g, FeS quantitatively immobilized Cd(II). Adsorption and CdS precipitation were responsible for Cd(II) uptake, with their relative importance depending on [Cd(II)] 0 /[FeS] 0 . At pH 5.5–6.0, adsorption was more important when [Cd(II)] 0 /[FeS] 0 ≤ 0.05 mmol/g. According to energy dispersive X-ray spectroscopy, Cd(II) exhibited strong spatial correlations with S and Cl. While Cd-S correlations corresponded to CdS precipitation and/or the surface complexation of Cd(II) with sulfhydryl functional sites, Cd–Cl correlations indicated the presence of chloride-complexed Cd(II). Given the strong correlations of both pairs, the adsorbed Cd(II) was likely present in chlorosulfide forms (e.g., ≡FeS–Cd(II)–Cl). When [Cd(II)] 0 /[FeS] 0 exceeded 0.05 mmol/g, CdS precipitation became more important. X-ray diffraction, transmission electron microscopy, and selected area electron diffraction revealed the formation of hawleyite (cubic CdS) at higher surface loadings. The Fe(II) species liberated during CdS precipitation were resorbed through adsorption at acidic pH and the formation of Fe (oxyhydr)oxides at neutral to basic pH. Given the greater stability of CdS than adsorbed Cd(II), the prevalence of the former suggests that FeS can serve as an effective reagent to remedy Cd(II) contamination under anoxic conditions. Due to its ubiquitous presence, FeS may also control the environmental fate and mobility of Cd(II) in sulfidic sediments.