Immobilization of Mercury by Carboxymethyl Cellulose Stabilized Iron Sulfide Nanoparticles: Reaction Mechanisms and Effects of Stabilizer and Water Chemistry

Iron sulfide (FeS) nanoparticles were prepared with sodium carboxymethyl cellulose (CMC) as a stabilizer, and tested for enhanced removal of aqueous mercury (Hg2+). CMC at ≥0.03 wt % fully stabilized 0.5 g/L of FeS (i.e., CMC-to-FeS molar ratio ≥0.0006). FTIR spectra suggested that CMC molecules were attached to the nanoparticles through bidentate bridging and hydrogen bonding. Increasing the CMC-to-FeS molar ratio from 0 to 0.0006 enhanced mercury sorption capacity by 20%; yet, increasing the ratio from 0.0010 to 0.0025 diminished the sorption by 14%. FTIR and XRD analyses suggested that precipitation (formation of cinnabar and metacinnabar), ion exchange (formation of Hg0.89Fe0.11S), and surface complexation were important mechanisms for mercury removal. A pseudo-second-order kinetic model was able to interpret the sorption kinetics, whereas a dual-mode isotherm model was proposed to simulate the isotherms, which considers precipitation and adsorption. High mercury uptake was observed over the pH range of 6.5–10.5, whereas significant capacity loss was observed at pH < 6. High concentrations of Cl– (>106 mg/L) and organic matter (5 mg/L as TOC) modestly inhibited mercury uptake. The immobilized mercury remained stable when preserved for 2.5 years at pH above neutral.