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

Abstract

Iron sulfide (FeS) nanoparticles were prepared with sodium carboxymethyl cellulose (CMC) as a stabilizer, and tested for enhanced removal of aqueous mercury (Hg(2+)). 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.