Sorption of mercuric ion by synthetic nanocrystalline mackinawite (FeS)

Iron sulfides are known to be efficient scavengers of heavy metals. In this study, Hg(II) sorption was investigated using synthetic nanocrystalline mackinawite (a disordered phase) as a function of initial Hg(II) concentration Hg(II)]0, initial FeS concentration FeS]0, total chloride concentration CIT, and pH. Hg(II) sorption mechanisms are dependent on relative concentrations of Hg(II)]0 and FeS]0 (the molar ratio of Hg(II)0/FeS]0). When the molar ratio of Hg(II)]0/FeS]o is as low as 0.05, adsorption is mainly responsible for Hg(II) removal, with its contribution to the overall sorption increasing at lower Cl(T). As the molar ratio increases, the adsorption capacity becomes saturated, resulting in precipitation of a sparingly soluble HgS(s). XRD analysis indicates formation of metacinnabar (beta-HgS). Concurrently with HgS(s) precipitation, the released Fe(II) from FeS(s) is resorbed by adsorption at acidic pH and either adsorption or precipitation as Fe (hydr)-oxides at neutral to basic pH. Subsequently, the Fe precipitate formed at neutral to basic pH serves as an adsorbent for Hg(II). Under the conditions where either adsorption or HgS(s) precipitation is dominant, more than 99% of Hg(II)]0 is immobilized. When the molar ratio of Hg(II)]0/FeS]0 exceeds 1, the sulfide concentration is no longer sufficient for HgS(s) precipitation, and formation of chloride salts (Hg2Cl2 at acidic pH and HgCl2 x 3HgO at basic pH) occurs.